WO2023232788A1 - Cosmetic hair treatment process, comprising a multi-application of a composition comprising amino acids and specific hydroxy carboxylic acids - Google Patents

Cosmetic hair treatment process, comprising a multi-application of a composition comprising amino acids and specific hydroxy carboxylic acids Download PDF

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Publication number
WO2023232788A1
WO2023232788A1 PCT/EP2023/064403 EP2023064403W WO2023232788A1 WO 2023232788 A1 WO2023232788 A1 WO 2023232788A1 EP 2023064403 W EP2023064403 W EP 2023064403W WO 2023232788 A1 WO2023232788 A1 WO 2023232788A1
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weight
notably
composition
chosen
better still
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PCT/EP2023/064403
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French (fr)
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Manon Chaumontet
Laura FENELON
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L'oreal
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/365—Hydroxycarboxylic acids; Ketocarboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A61K8/447—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof containing sulfur
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair

Definitions

  • TITLE Cosmetic hair treatment process, comprising a multi-application of a composition comprising amino acids and specific hydroxy carboxylic acids
  • the present invention relates to a cosmetic hair treatment process, comprising at least two successive steps of applying a composition comprising one or more compounds of amino acid type and one or more specific hydroxy carboxylic acids.
  • Mineral waters contain, for example, variable amounts of minerals present in the form of dissolved ions, such as calcite (present in the form of calcium), dolomite (present in the form of calcium and magnesium), magnetite (present in the form of iron) and chalcanthite (present in the form of copper).
  • calcite present in the form of calcium
  • dolomite present in the form of calcium and magnesium
  • magnetite present in the form of iron
  • chalcanthite present in the form of copper
  • “Hard” waters are also concentrated in minerals, such as calcium and magnesium, and swimming pool waters are for their part concentrated in copper salts originating from algicides used in the treatment of swimming pools.
  • Hair has a strong tendency to absorb these minerals and/or their metal salts because of the presence, at the surface thereof, of anionic functional groups which correspond in particular to the sulfonic or carboxylic functional groups of keratin. Furthermore, the isoelectric point of the individual hair is generally described between 3.2 and 4. The result of this is that, in everyday life, the pH of the water applied to the hair is greater than such values, which results in a negatively charged fibre.
  • the accumulation of the metal (iron, copper, for example) salts can accelerate the damage caused to the hair because they catalyse oxidation/reduction reactions and generate hydroxyl radicals HO° which can be harmful to the keratin fibre, including at low contents.
  • the hair can become less resistant, more weakened, indeed even break more easily, or also lose its sheen, due to the accumulation of minerals and/or their metal salts.
  • One subject of the present invention is thus a cosmetic hair treatment process, comprising at least two successive steps of applying a cosmetic composition comprising:
  • hydroxylated polycarboxylic acids comprising from 2 to 8 carbon atoms, and/or salts thereof, present in a total content of at least 0.5% by weight, relative to the total weight of the composition.
  • the process according to the invention makes it possible to improve the resistance to breakage of the hair, to strengthen the hair and also to significantly limit its reduction or loss of sheen, undesirable effects liable to be caused by the presence of metal ions, notably copper or calcium ions, within said fibres.
  • the fibres After performing the process, the fibres appear to be strengthened, said strengthening being improved with successive applications of the composition.
  • composition used in the context of the invention makes it possible to contribute conditioning properties to the hair, notably a smooth feel, softness, sheen and facilitated disentangling, and to do so while contributing strength, body and a bulk effect to the head of hair.
  • the process according to the invention is particularly suitable for hair that has been sensitized, weakened and/or damaged, notably as a result of physical (repeated brushing) and/or chemical treatments, for example dyeing, bleaching, perming and/or straightening.
  • the hair treatment process according to the invention comprises at least two successive steps consisting in applying the composition as defined above to the hair.
  • the composition is applied to the hair several times successively, that is to say that the steps of applying the composition according to the invention are performed one after the other with or without an intermediate rinsing step.
  • the process according to the invention involves a step of rinsing the hair at least between two successive steps of applying the composition.
  • the leave-on time of the composition according to the invention on the hair can vary between several seconds (10 seconds for example) and several minutes (5 to 60 minutes for example), preferably between 1 and 30 minutes, better still between 2 and 15 minutes.
  • the application to the hair may be performed for example by means of a comb, a fine brush, with the aid of a coarse brush or with the fingers.
  • the hair may be rinsed and/or may be dried.
  • the rinsing may be performed with water or a shampoo, after a possible leave-on time.
  • the hair can then be squeezed dry, optionally washed using a standard shampoo and then dried.
  • the rinsing step may also be followed by a drying step, for example at room temperature (25°C) or at a temperature greater than 40°C.
  • a drying step for example at room temperature (25°C) or at a temperature greater than 40°C.
  • the hair is dried, in addition to a supply of heat, with a flow of air.
  • a mechanical action may be exerted on the locks, such as combing, brushing, or running the fingers through.
  • the drying step of the process of the invention may be performed with a hood, a hairdryer or a straightening iron.
  • the drying temperature is between 40°C and 110°C, preferably between 50°C and 90°C.
  • the drying temperature is between 110°C and 220°C, preferably between 130°C and 200°C.
  • the hair treatment process according to the invention may comprise more than two successive steps of applying the composition as defined above to the hair, for example at least 3 successive steps, or even at least 4 successive steps. These successive applications may also be performed over several weeks, or even several months.
  • the time between each application step may advantageously be between 1 day and several days, for example 1 day to 7 days, which corresponds to a weekly application of the composition, or between 2 and 4 days, which corresponds to a twice-weekly application of the composition.
  • composition used in the context of the present invention comprises one or more compounds of amino acid type.
  • the term “compound of amino acid type” means an organic compound comprising one or more carboxylic acid and/or sulfonic acid functions and one or more amine functions, it being possible for the amine function(s) to be endocyclic, optionally in salt form.
  • the compound(s) of amino acid type are chosen from compounds of amino acid type comprising only one or more carboxylic acid functions (thus not comprising any sulfonic acid functions) and/or salts thereof.
  • Said compounds are also called compounds of aminocarboxylic acid type and are particularly preferred.
  • composition according to the present invention comprises one or more compounds of amino acid type chosen from the compounds corresponding to formula (I) below and/or salts thereof.
  • the compounds of amino acid type may thus correspond to formula (I): in which p is an integer equal to 1 or 2, it being understood that:
  • R forms, with the nitrogen atom, a saturated heterocycle comprising from 5 to 8 ring members, preferably 5 ring members, it being possible for this ring to be substituted with one or more groups chosen from hydroxyl or (Ci-C4)alkyl;
  • R represents a hydrogen atom or a saturated, linear or branched, (Ci- Ci2)alkyl, preferably (Ci-C4)alkyl, group, optionally interrupted with one or more heteroatoms or groups chosen from -S-, -NH- or -C(NH)- and/or optionally substituted with one or more groups chosen from hydroxyl (-OH), amino (-NH2), - SH, -COOH, -CONH2 or -NH-C(NH)-NH 2 .
  • R forms, with the nitrogen atom, a saturated heterocycle comprising 5 ring members, this ring not being substituted.
  • p 2.
  • R represents a hydrogen atom or a saturated, linear or branched, (Ci-C4)alkyl group, optionally interrupted with a -S- heteroatom and/or optionally substituted with one or two groups chosen from hydroxyl, amino or -NH- C(NH)-NH 2 .
  • p 2 and R represents a hydrogen atom.
  • the compounds of amino acid type may also be a salt of a compound of formula (I).
  • These salts comprise the salts with organic or mineral bases, for example the salts of alkali metals, for instance the lithium, sodium or potassium salts; the salts of alkaline-earth metals, for instance the magnesium or calcium salts, and the zinc salts.
  • the compounds of amino acid type may be in the form of an optical isomer of L, D or DL configuration, preferably of L configuration.
  • the compound(s) of amino acid type according to the invention are chosen from glycine, proline, methionine, serine, arginine, lysine, their salts (notably alkali metal, alkaline-earth metal or zinc salts) and mixtures thereof.
  • the compound(s) of amino acid type according to the invention are chosen from glycine, proline, methionine, serine, arginine, salts thereof and mixtures thereof.
  • the compound of amino acid type is chosen from glycine, salts thereof (notably alkali metal, alkaline-earth metal or zinc salts) and mixtures thereof.
  • glycine salts As glycine salts according to the present invention, mention may be made of sodium glycinate, zinc glycinate, calcium glycinate, magnesium glycinate, manganese glycinate and potassium glycinate, preferably sodium glycinate and potassium glycinate.
  • the compound of amino acid type is glycine.
  • the total content of compound(s) of amino acid type present in the composition according to the invention is at least 0.6% by weight, relative to the total weight of the composition. This content may range from 0.6% to 10% by weight, notably from 0.7% to 8% by weight, better still from 0.8% to 7% by weight, relative to the total weight of the composition. In particular, the total content of compound(s) of aminocarboxylic acid type in the composition according to the invention may range from 0.6% to 10% by weight, notably from 0.7% to 8% by weight, better still from 0.8% to 7% by weight, relative to the total weight of the composition.
  • the total content of compound(s) of amino acid type chosen from glycine, proline, methionine, serine, arginine, lysine, salts thereof and mixtures thereof in the composition according to the invention may range from 0.6% to 10% by weight, notably from 0.7% to 8% by weight, better still from 0.8% to 7% by weight, relative to the total weight of the composition.
  • the total content of compound(s) of amino acid type chosen from glycine, salts thereof and mixtures thereof in the composition according to the invention may range from 0.6% to 10% by weight, notably from 0.7% to 8% by weight, better still from 0.8% to 7% by weight, relative to the total weight of the composition.
  • the glycine content in the composition according to the invention may range from 0.6% to 10% by weight, notably from 0.7% to 8% by weight, better still from 0.8% to 7% by weight, relative to the total weight of the composition.
  • composition used according to the invention also comprises one or more hydroxylated polycarboxylic acids comprising from 2 to 8 carbon atoms, and/or salts thereof.
  • polyacids are different from the compounds of amino acid type described above.
  • Said polyacids comprise at least two COOH groups (in acid or salified form); they may comprise two to three COOH groups (in acid or salified form).
  • They also comprise at least one OH group but may comprise several thereof, notably from two to three OH groups.
  • they comprise in total from four to six carbon atoms and their hydrocarbon-based chain is saturated and linear.
  • the hydroxylated polycarboxylic acids and/or salts thereof comprise in total from four to six carbon atoms, from one to three OH groups and from two to three COOH groups (in acid or salified form).
  • the salts of these polyacids comprise the salts with organic or mineral bases, for example the salts of alkali metals, such as the lithium, sodium or potassium salts; the salts of alkaline-earth metals, such as the magnesium or calcium salts, and the zinc salts.
  • alkali metal or alkaline-earth metal salts are preferred and in particular the sodium salts.
  • the hydroxylated polycarboxylic acids or salts thereof are chosen from a-hydroxy acids and salts thereof, and notably from tartaric acid or citric acid, and salts thereof, notably alkali metal or alkaline-earth metal salts; most particularly sodium citrate and/or sodium tartrate; better still citric acid or salts thereof, notably alkali metal or alkaline-earth metal salts, such as sodium citrate.
  • the total content of hydroxylated polycarboxylic acids comprising in total from two to eight carbon atoms, and/or salts thereof, present in the composition according to the invention is at least 0.5% by weight, relative to the total weight of the composition. This content may range from 0.5% to 10% by weight, notably from 1 % to 8% by weight, better still from 1.5% to 6% by weight, relative to the total weight of the composition.
  • the total content of hydroxylated polycarboxylic acids comprising in total from four to six carbon atoms, from one to three OH groups and two or three COOH groups, or salts thereof, present in the composition according to the invention may range from 0.5% to 10% by weight, notably from 1 % to 8% by weight, better still from 1 .5% to 6% by weight, relative to the total weight of the composition.
  • the total content of hydroxylated polycarboxylic acids chosen from tartaric acid and/or citric acid, and salts thereof, notably alkali metal or alkaline-earth metal salts, in the composition according to the invention may range from 0.5% to 10% by weight, notably from 1 % to 8% by weight, better still from 1.5% to 6% by weight, relative to the total weight of the composition.
  • the content of citric acid and/or salts thereof in the composition according to the invention may range from 0.5% to 10% by weight, notably from 1 % to 8% by weight, better still from 1.5% at 6% by weight, relative to the total weight of the composition.
  • composition used according to the invention may optionally comprise one or more associative polymers.
  • the associative polymers are nonionic.
  • the term “polymer” means any compound derived from the polymerization by polycondensation or from the radical polymerization of monomers, at least one of which is other than an alkylene oxide, and of a monofunctional compound of formula RX, R denoting an optionally hydroxylated C10-C30 alkyl or alkenyl group, and X denoting a carboxylic acid, amine, amide, hydroxyl or ester group. All the compounds resulting solely from the simple condensation of an alkylene oxide with a fatty alcohol, a fatty ester, a fatty acid, a fatty amide or a fatty amine are in particular excluded.
  • the term “associative polymer” means an amphiphilic polymer that is capable, in an aqueous medium, of reversibly combining with itself or with other molecules. It generally includes, in its chemical structure, at least one hydrophilic region or group and at least one hydrophobic region or group.
  • the associative polymers according to the invention are polymers comprising at least one fatty chain including from 8 to 30 carbon atoms, the molecules of which are capable, in the formulation medium, of combining with each other or with molecules of other compounds.
  • the fatty chain includes from 10 to 30 carbon atoms.
  • amphiphilic polymers that is to say polymers including one or more hydrophilic parts or groups which make them water- soluble and one or more hydrophobic regions or groups (including at least one fatty chain) via which the polymers interact and assemble with each other or with other molecules.
  • hydrophobic group means a group or a polymer containing a saturated or unsaturated, linear or branched hydrocarbon-based chain, which may contain one or more heteroatoms such as P, O, N or S, or a radical containing a perfluoro or silicone chain.
  • the hydrophobic group includes at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and preferentially from 18 to 30 carbon atoms.
  • the hydrocarbon-based hydrophobic group originates from a monofunctional compound.
  • the hydrophobic group may be derived from a fatty alcohol, such as stearyl alcohol, dodecyl alcohol or decyl alcohol, or else from a polyalkylenated fatty alcohol, such as Steareth-100. It may also denote a hydrocarbon-based polymer, for instance polybutadiene.
  • fatty chain means a linear or branched alkyl or alkenyl chain including at least 8 carbon atoms, preferably from 8 to 30 carbon atoms and better still from 10 to 22 carbon atoms.
  • fatty compound for instance a fatty alcohol, a fatty acid or a fatty amide, means a compound comprising, in its main chain, at least one saturated or unsaturated hydrocarbon-based chain, such as an alkyl or alkenyl chain, including at least 8 carbon atoms, preferably from 8 to 30 carbon atoms and better still from 10 to 22 carbon atoms.
  • anionic associative polymers mention may notably be made of:
  • anionic associative polymers preference is particularly given to polymers formed from 20% to 60% by weight of acrylic acid and/or of methacrylic acid, from 5% to 60% by weight of C1-C4 alkyl (meth)acrylates, from 2% to 50% by weight of fatty-chain allyl ether of formula (I’) and from 0% to 1 % by weight of a crosslinking agent which is preferably a copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylenebisacrylamide.
  • a crosslinking agent which is preferably a copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene
  • Stepth- 10 crosslinked terpolymers of methacrylic acid, of ethyl acrylate and of polyethylene glycol (10 EO) stearyl alcohol ether (Steareth- 10), notably the product sold by the company BASF under the name Salcare SC80, which is a 30% aqueous emulsion of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate and of Steareth-10 allyl ether (40/50/10) having the INCI name Steareth-10 Allyl Ether/Acrylates Copolymer;
  • Salcare SC80 polyethylene glycol (10 EO) stearyl alcohol ether
  • These polymers are preferably chosen from those for which the hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the monomer of formula (II) below: in which R1 denotes H or CH3 or C2H5, and for which the hydrophobic unit of (C10- C3o)alkyl ester of unsaturated carboxylic acid type corresponds to the monomer of formula (III) below: in which R2 denotes H, CH3 or C2H5 and R3 denotes a C10-C30 and preferably C12- C22 alkyl radical.
  • Alkyl esters of unsaturated carboxylic acids in accordance with the invention comprise, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.
  • anionic associative polymers use will more particularly be made of polymers formed from a mixture of monomers comprising: (i) (meth)acrylic acid, (ii) an ester of formula (III) described above and in which R2 denotes H or CH3 and R3 denotes an alkyl radical containing from 12 to 22 carbon atoms, and optionally (iii) a crosslinking agent which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate and methylenebisacrylamide.
  • a crosslinking agent which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate and methylenebisacrylamide.
  • anionic associative polymers of this type preference is more particularly given, to those constituted of from 95% to 60% by weight of (meth)acrylic acid, 4% to 40% by weight of C10-C30 alkyl acrylate and 0% to 6% by weight of crosslinking polymerizable monomer, or else to those constituted of from 98% to 96% by weight of (meth)acrylic acid, 1 % to 4% by weight of C10-C30 alkyl acrylate and 0.1 % to 0.6% by weight of crosslinking polymerizable monomer, such as those described previously.
  • Pemulen TR1 Pemulen TR2
  • Carbopol 1382 Carbopol ETD 2020
  • Carbopol Ultrez 20 Carbopol Ultrez 21
  • INCI name Acrylates/C I Q- 30 Alkyl Acrylate Crosspolymer having the INCI name Acrylates/C I Q- 30 Alkyl Acrylate Crosspolymer, and even more preferably Pemulen TR1 and Carbopol 1382;
  • acrylic terpolymers comprising (a) from 20% to 70% by weight of an a,(3- monoethylenically unsaturated carboxylic acid, (b) from 20% to 80% by weight of a non-surface-active a,[3-monoethylenically unsaturated monomer other than (a), and (c) from 0.5% to 60% by weight of a nonionic monourethane which is the reaction product of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate.
  • ethoxylated (40 EO) behenyl alcohol terpolymer notably as a 25% aqueous dispersion, such as the product Viscophobe DB1000 sold by the company Amerchol (Dow Chemical), having the INC name Polyacrylate-3;
  • copolymers including among their monomers (i) an a,p-monoethylenically unsaturated carboxylic acid, such as acrylic or methacrylic acid, and (ii) an ester of an a,p-monoethylenically unsaturated carboxylic acid, notably acrylic or methacrylic acid, and of fatty alcohol, notably C8-C32 fatty alcohol, which is oxyalkylenated, notably comprising from 2 to 100 mol of ethylene oxide, in particular from 4 to 50, or even from 10 to 40 EO.
  • an a,p-monoethylenically unsaturated carboxylic acid such as acrylic or methacrylic acid
  • an ester of an a,p-monoethylenically unsaturated carboxylic acid notably acrylic or methacrylic acid
  • fatty alcohol notably C8-C32 fatty alcohol, which is oxyalkylenated, notably comprising from 2 to 100 mol of ethylene oxide, in particular
  • these compounds also comprise, as monomer, an ester of an a,(3- monoethylenically unsaturated carboxylic acid and of a C1-C4 alcohol, notably a C1- C4 alkyl (meth)acrylate.
  • these copolymers comprise at least one (meth)acrylic acid monomer, at least one C1-C4 alkyl (meth)acrylate monomer and at least one C8-C32 alkyl (meth)acrylate monomer which is oxyethylenated, comprising from 2 to 100 mol EO, in particular from 4 to 50 EO, or even from 10 to 40 EO.
  • Aculyn 22 sold by the company Rohm and Haas, which is an oxyalkylenated methacrylic acid/ethyl acrylate/stearyl methacrylate terpolymer (INCI name: Acrylates/Steareth-20 Methacrylate Copolymer), or also of Aculyn 28 sold by Rohm and Haas, which is an oxyalkylenated methacrylic acid/ethyl acrylate/behenyl methacrylate terpolymer (INCI name: Acrylates/Beheneth-25 Methacrylate Copolymer), and also of the Novethix L-10 Polymer sold by Lubrizol;
  • - terpolymers including from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of AMPS units and from 5 mol% to 80 mol% of n-(C6-C8)alkylacrylamide units, such as those described in patent US 5 089 578;
  • Aristoflex HMS® sold by the company Clariant (INCI name: Ammonium Acryloyldimethyltaurate/Steareth-25 Methacrylate Crosspolymer), or beheneth-25 methacrylate units, such as Aristoflex HMB (INCI name: Ammonium Acryloyldimethyltaurate/Beheneth-25 Methacrylate Crosspolymer) sold by the company Clariant, or also steareth-8 methacrylate units, such as Aristoflex SNC® from Clariant (INCI name: Ammonium Acryloyldimethyltaurate/Steareth-8 Methacrylate Copolymer);
  • G associative polymers including at least one vinyllactam monomer and at least one a,p-monoethylenically unsaturated carboxylic acid monomer, such as terpolymers of vinylpyrrolidone, of acrylic acid and of C1-C20 alkyl methacrylate, for example lauryl methacrylate, such as the product sold by the company ISP under the name Acrylidone® LM (INCI name: VP/Acrylates/Lauryl Methacrylate Copolymer).
  • cationic associative polymers mention may be made of:
  • R and R’ which may be identical or different, represent a hydrophobic group or a hydrogen atom
  • X and X’ which may be identical or different, represent a group including an amine function optionally bearing a hydrophobic group, or alternatively a group L”;
  • L, L’ and L which may be identical or different, represent a group derived from a diisocyanate
  • P and P’ which may be identical or different, represent a group including an amine function optionally bearing a hydrophobic group
  • Y represents a hydrophilic group
  • r is an integer between 1 and 100 inclusive, preferably between 1 and 50 inclusive and in particular between 1 and 25 inclusive
  • n, m and p are each, independently of each other, between 0 and 1000 inclusive; the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group.
  • the only hydrophobic groups are the groups R and R' at the chain ends.
  • One preferred family of cationic associative polyurethanes is the one corresponding to formula (la) described above, in which:
  • R and R’ both independently represent a hydrophobic group
  • X and X’ each represent a group L”, n and p are integers that are between 1 and 1000 inclusive, and
  • L, L’, L”, P, P’, Y and m have the meanings given above.
  • R and R’ both independently represent a hydrophobic group
  • L, L’, Y and m have the meaning indicated above.
  • the number-average molecular mass (Mn) of the cationic associative polyurethanes is preferably between 400 and 500 000 inclusive, in particular between 1000 and 400 000 inclusive and ideally between 1000 and 300 000 inclusive.
  • the hydrocarbon-based group originates from a monofunctional compound.
  • the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, for instance polybutadiene.
  • X and/or X’ denote(s) a group including a tertiary or quaternary amine
  • X and/or X’ may represent one of the following formulae: in which:
  • R2 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally including a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, 0 and P;
  • R1 and R3 which may be identical or different, denote a linear or branched C1-C30 alkyl or alkenyl radical or an aryl radical, at least one of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, 0 and P;
  • A- is a physiologically acceptable anionic counterion, such as a halide, for instance a chloride or bromide, or a mesylate.
  • Z represents -O-, -S- or -NH-
  • R4 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally including a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, 0 and P.
  • the groups P and P’ comprising an amine function may represent at least one of the following formulae: in which:
  • R10 represents a linear or branched, optionally unsaturated alkylene group possibly containing one or more heteroatoms chosen from N, 0, S and P;
  • A- is a physiologically acceptable anionic counterion, such as a halide, for instance chloride or bromide, or mesylate.
  • hydrophilic group means a polymeric or non-polymeric water-soluble group.
  • hydrophilic polymer When it is a hydrophilic polymer, mention may be made, for example, of polyethers, sulfonated polyesters and sulfonated polyamides, or a mixture of these polymers.
  • the hydrophilic compound is preferentially a polyether and notably a poly(ethylene oxide) or polypropylene oxide).
  • the cationic associative polyurethanes of formula (la) are formed from diisocyanates and from various compounds bearing functions containing labile hydrogen.
  • the functions containing labile hydrogen may be alcohol, primary or secondary amine or thiol functions, giving, after reaction with the diisocyanate functions, polyurethanes, polyureas and polythioureas, respectively.
  • the term “polyurethanes” encompasses these three types of polymer, namely polyurethanes per se, polyureas and polythioureas, and also copolymers thereof.
  • a first type of compound involved in the preparation of the polyurethane of formula (la) is a compound including at least one unit bearing an amine function.
  • This compound may be multifunctional, but the compound is preferentially difunctional, that is to say that, according to a preferential embodiment, this compound includes two labile hydrogen atoms borne, for example, by a hydroxyl, primary amine, secondary amine or thiol function.
  • a mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low may also be used.
  • this compound may include more than one unit containing an amine function.
  • it is a polymer bearing a repetition of the unit containing an amine function.
  • HZ-(P) n -ZH or HZ-(P’) P -ZH in which Z, P, P’, n and p are as defined above.
  • Examples that may be mentioned include N-methyldiethanolamine, N-tert- butyldiethanolamine and N-sulfoethyldiethanolamine.
  • methylenediphenyl diisocyanate By way of example, mention may be made of methylenediphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, butane diisocyanate and hexane diisocyanate.
  • a third compound involved in the preparation of the polyurethane of formula (la) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (la).
  • This compound is constituted of a hydrophobic group and a function containing a labile hydrogen, for example a hydroxyl, primary or secondary amine, or thiol function.
  • this compound may be a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol.
  • this compound may be, for example, a-hydroxylated hydrogenated polybutadiene.
  • the hydrophobic group of the polyurethane of formula (la) may also result from the quaternization reaction of the tertiary amine of the compound including at least one tertiary amine unit.
  • the hydrophobic group is introduced via the quaternizing agent.
  • This quaternizing agent is a compound of the type RQ or R'Q, in which R and R' are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.
  • the cationic associative polyurethane may also comprise a hydrophilic block.
  • This block is provided by a fourth type of compound involved in the preparation of the polymer.
  • This compound may be multifunctional. It is preferably difunctional. It is also possible to have a mixture in which the percentage of multifunctional compound is low.
  • the functions containing labile hydrogen are alcohol, primary or secondary amine or thiol functions. This compound may be a polymer terminated at the chain ends with one of these functions containing labile hydrogen.
  • hydrophilic polymer when it is not a polymer, mention may be made of ethylene glycol, diethylene glycol and propylene glycol.
  • hydrophilic polymer mention may be made, for example, of polyethers, sulfonated polyesters and sulfonated polyamides, or a mixture of these polymers.
  • the hydrophilic compound is preferentially a polyether and in particular a poly(ethylene oxide) or polypropylene oxide).
  • the hydrophilic group termed Y in formula (la) is optional. Specifically, the units containing a quaternary or protonated amine function may suffice to provide the solubility or water-dispersibility required for this type of polymer in an aqueous solution.
  • hydrophilic group Y is optional, cationic associative polyurethanes including such a group are, however, preferred.
  • quaternized celluloses modified with groups including at least one fatty chain such as linear or branched alkyl, linear or branched arylalkyl or linear or branched alkylaryl groups including at least 8 carbon atoms, or mixtures thereof;
  • R and R’ which may be identical or different, represent an ammonium group - R a RbRcN + Q- in which R a , Rb and R c , which may be identical or different, represent a hydrogen atom or a linear or branched C1-C30, preferentially C1-C20, alkyl group, such as methyl or dodecyl; and Q’ represents an anionic counterion, such as a halide, for instance a chloride or bromide; and n, x and y, which may be identical or different, represent an integer between 1 and 10 000.
  • the alkyl radicals borne by the above quaternized celluloses i) or hydroxyethylcelluloses ii) preferably include from 8 to 30 carbon atoms.
  • the aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.
  • Quatrisoft LM 200® sold by the company Amerchol/Dow Chemical
  • Crodacel QM® INCI name: PG-Hydroxyethylcellulose cocodimonium chloride
  • R represents a trimethylammonium halide and R’ represents a dimethyldodecylammonium halide; more preferentially, R represents trimethylammonium chloride -(CH3)3N + CI’ and R’ represents dimethyldodecylammonium chloride -(CH3)2(Ci2H25)N + CI’.
  • This type of polymer is known under the trade name Softcat Polymer SL®, such as SL-100, SL-60, SL-30 and SL-5, from the company Amerchol/Dow Chemical, having the INCI name Polyquaternium-67.
  • the polymers of formula (lb) are those of which the viscosity is between 2000 and 3000 cPs inclusive. Preferentially, the viscosity is between 2700 and 2800 cPs inclusive.
  • Softcat Polymer SL-5 has a viscosity of 2500 cPs
  • Softcat Polymer SL-30 has a viscosity of 2700 cPs
  • Softcat Polymer SL-60 has a viscosity of 2700 cPs
  • Softcat Polymer SL-100 has a viscosity of 2800 cPs.
  • X denotes an oxygen atom or an NR6 radical
  • Ri and Re denote, independently of each other, a hydrogen atom or a linear or branched C1-C5 alkyl radical
  • R2 denotes a linear or branched C1-C4 alkyl radical
  • R3, R4 and Rs denote, independently of each other, a hydrogen atom, a linear or branched C1-C30 alkyl radical or a radical of formula (lllc): in which:
  • Y1 and Y2 denote, independently of each other, a linear or branched C2-C16 alkylene radical
  • R7 denotes a hydrogen atom, or a linear or branched C1-C4 alkyl radical or a linear or branched C1-C4 hydroxyalkyl radical
  • Rs denotes a hydrogen atom or a linear or branched C1-C30 alkyl radical
  • p, q and r denote, independently of each other, either the value zero or the value 1
  • m and n denote, independently of each other, an integer ranging from 0 to 100 inclusive
  • x denotes an integer ranging from 1 to 100 inclusive
  • Z denotes an anionic counterion of an organic or mineral acid, such as a halide, for instance chloride or bromide, or mesylate; with the proviso that:
  • R3, R4, R5 or R8 denotes a linear or branched C9- C30 alkyl radical
  • the cationic poly(vinyllactam) polymers according to the invention may be crosslinked or noncrosslinked and may also be block polymers.
  • the counterion Z’ of the monomers of formula (Ic) is chosen from halide ions, phosphate ions, the methosulfate ion and the tosylate ion.
  • R3, R4 and Rs denote, independently of each other, a hydrogen atom or a linear or branched C1-C30 alkyl radical.
  • the monomer b) is a monomer of formula (Ic) for which, preferentially, m and n are equal to 0.
  • the vinyllactam or alkylvinyllactam monomer is preferably a compound of structure (IVc): in which s denotes an integer ranging from 3 to 6; R9 denotes a hydrogen atom or a linear or branched C1-C5 alkyl radical and R10 denotes a hydrogen atom or a linear or branched C1-C5 alkyl radical, with the proviso that one at least of the radicals R9 and R10 denotes a hydrogen atom.
  • the monomer (IVc) is vinylpyrrolidone.
  • the cationic poly(vinyllactam) polymers according to the invention may also contain one or more additional monomers, preferably cationic or nonionic monomers.
  • terpolymers comprising, by weight, 40% to 95% of monomer (a), 0.1 % to 55% of monomer (c) and 0.25% to 50% of monomer (b) will be used.
  • Such polymers are notably described in patent application WO-OO/68282.
  • cationic poly(vinyllactam) polymers use is in particular made of: vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethyl- methacrylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethyl- methacrylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethyl- methacrylamidopropylammonium tosylate or chloride terpolymers.
  • the vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethylacrylami dopropylammonium chloride terpolymer is notably sold by the company ISP under the names Styleze W10® and Styleze W20L® (INCI name: Polyquaternium-55).
  • the weight-average molecular mass (Mw) of the cationic poly(vinyllactam) polymers is preferably between 500 and 20 000 000, more particularly between 200 000 and 2 000 000 and preferentially between 400 000 and 800 000.
  • the cationic polymers obtained by polymerization of a mixture of monomers comprising one or more vinyl monomers substituted with one or more amino groups, one or more hydrophobic nonionic vinyl monomers and one or more associative vinyl monomers, such as described in patent application WO 2004/024779.
  • Such a polymer is, for example, the compound sold by the company Lubrizol under the name Carbopol Aqua CC® and which corresponds to the INCI name Polyacrylate-1 Crosspolymer.
  • the nonionic associative polymers are preferably chosen, alone or as a mixture, from:
  • hydroxyethylcelluloses modified with groups including at least one fatty chain, notably C8-C32 and better still C14-C28 alkyl, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22, for instance the cetylhydroxyethylcellulose sold notably under the reference Natrosol Plus Grade 330 CS (C16 alkyls) sold by the company Ashland, or the product Polysurf 67CS sold by the company Ashland,
  • polyalkylene glycol alkylphenol ether groups such as the product Amercell Polymer HM-1500 (polyethylene glycol (15) nonylphenol ether) sold by the company Amerchol, - and mixtures thereof.
  • copolymers of vinylpyrrolidone and of fatty-chain hydrophobic monomers notably C8-C32 and better still C14-C28 alkyl. Examples that may be mentioned include:
  • polyurethane polyethers including in their chain both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks, which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences;
  • polymers comprising an aminoplast ether backbone having at least one fatty chain, notably C8-C32 and better still C14-C28 alkyl, such as the Pure Thix compounds sold by the company Sud-Chemie.
  • the polyurethane polyethers include at least two hydrocarbon-based lipophilic chains containing from 8 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon-based chains possibly being pendent chains or chains at the end of the hydrophilic block.
  • the polymer may include a hydrocarbon-based chain at one end or at both ends of a hydrophilic block.
  • the polyurethane polyethers may be multiblock, in particular in triblock form.
  • the hydrophobic blocks may be at each end of the chain (for example: triblock copolymer bearing a hydrophilic central block) or distributed both at the ends and in the chain (for example, multiblock copolymer). These same polymers may also be graft polymers or star polymers.
  • the fatty-chain nonionic polyurethane polyethers may be triblock copolymers, the hydrophilic block of which is a polyoxyethylenated chain including from 50 to 1000 oxyethylene groups.
  • the nonionic polyurethane polyethers include a urethane bond between the hydrophilic blocks, whence arises the name.
  • nonionic fatty-chain polyurethane polyethers include those in which the hydrophilic blocks are linked to the lipophilic blocks via other chemical bonds.
  • nonionic fatty-chain polyurethane polyethers that may be used in the invention, use may also be made of Rheolate 205® bearing a urea function, sold by the company Rheox, or Rheolate® 208, 204 or 212, and also Acrysol RM 184®. Mention may also be made of the product Elfacos T210® containing a C12-C14 alkyl chain, and the product Elfacos T212® containing a C18 alkyl chain, from Akzo. The product DW 1206B® from Rohm & Haas having a C20 alkyl chain and having a urethane bond, provided at a solids content of 20% in water, can also be used.
  • Use may also be made of solutions or dispersions of these polymers, in particular in water or in an aqueous/alcoholic medium. Mention may be made, as examples of such polymers, of Rheolate® 255, Rheolate® 278 and Rheolate® 244, sold by the company Rheox. Use may also be made of the products DW 1206F and DW 1206J sold by the company Rohm & Haas.
  • polyurethane polyethers that may be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci. 271 , 380.389 (1993).
  • a polyurethane polyether that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate.
  • Aculyn 46® is a polycondensate of polyethylene glycol having 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81 %);
  • Aculyn 44® is a polycondensate of polyethylene glycol having 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%)].
  • the composition comprises one more or nonionic associative polymers, preferentially chosen from polyurethane polyethers.
  • the associative polymer(s) are present in the composition in a total content ranging from 0.01 % to 10% by weight, preferentially from 0.05% to 5% by weight, more preferentially from 0.1 % to 1 .5% by weight, relative to the total weight of the composition.
  • the nonionic associative polymer(s) are present in the composition in a total content ranging from 0.01 % to 10% by weight, preferentially from 0.05% to 5% by weight, more preferentially from 0.1 % to 1.5% by weight, relative to the total weight of the composition.
  • the nonionic associative polymer(s) chosen from polyether polyurethanes are present in the composition in a total content ranging from 0.01 % to 10% by weight, preferentially from 0.05% to 5% by weight, more preferentially from 0.1 % to 1 .5% by weight, relative to the total weight of the composition.
  • composition used according to the invention may optionally comprise one or more silicones, which may be chosen in particular from amino silicones, non-amino silicones and mixtures thereof.
  • composition according to the invention may thus comprise one or more non- amino silicones, which may be solid or liquid, preferably liquid (at 25°C, 1 atm), and volatile or non-volatile.
  • non-amino silicones that may be used may be soluble or insoluble in the composition according to the invention; they may be in oil, wax, resin or gum form; silicone oils and gums are preferred.
  • the volatile silicones may be chosen from those with a boiling point of between 60°C and 260°C (at atmospheric pressure) and in particular from: i) cyclic polydialkylsiloxanes including from 3 to 7 and preferably 4 to 5 silicon atoms, such as
  • cyclic silicones with silicon-derived organic compounds such as the mixture of octamethylcyclotetrasiloxane and of tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and of 1 ,1’- oxy(2,2,2’,2’,3,3’-hexatrimethylsilyloxy)bisneopentane; ii) linear polydialkylsiloxanes containing 2 to 9 silicon atoms, which generally have a viscosity of less than or equal to 5x1 O’ 6 m 2 /s at 25°C, such as decamethyltetrasiloxane.
  • non-volatile silicones mention may be made, alone or as a mixture, of polydialkylsiloxanes and notably polydimethylsiloxanes (PDMS or dimethicone), polydiarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, and also nonamino organopolysiloxanes (or organomodified polysiloxanes, or alternatively organomodified silicones) which are polysiloxanes including in their structure one or more non-amino organofunctional groups, generally attached via a hydrocarbon- based group, and preferably chosen from aryl groups, alkoxy groups and polyoxyethylene and/or polyoxypropylene groups.
  • PDMS or dimethicone polydimethylsiloxanes
  • polyalkylarylsiloxanes silicone gums and resins
  • nonamino organopolysiloxanes or organomodified polysiloxanes, or alternatively organomod
  • the organomodified silicones may be polydiarylsiloxanes, notably polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned previously.
  • the polyalkylarylsiloxanes are particularly chosen from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes.
  • organopolysiloxanes including:
  • polyoxyethylene and/or polyoxypropylene groups optionally including C6-C24 alkyl groups, such as dimethicone copolyols, and notably those sold by the company Dow Coming under the name DC 1248 or the oils Silwet® L 722, L 7500, L 77 and L 711 from the company Union Carbide; or alternatively (Ci2)alkylmethicone copolyols, and notably those sold by the company Dow Coming under the name Q2-5200;
  • hydroxylated groups for instance polyorganosiloxanes bearing a hydroxyalkyl function
  • the silicones can also be chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes having trimethylsilyl end groups (CTFA: dimethicone).
  • CTFA trimethylsilyl end groups
  • polydialkylsiloxanes mention may be made of the following commercial products:
  • oils of the 200 series from Dow Corning such as DC200 with a viscosity of 60 000 mm 2 /s;
  • CTFA dimethiconol
  • oils of the 48 series from Rhodia are examples of polydimethylsiloxanes having dimethylsilanol end groups (CTFA: dimethiconol), such as the oils of the 48 series from Rhodia.
  • Products that may be used more particularly in accordance with the invention are mixtures such as:
  • CTFA dimethiconol
  • CFA cyclic polydimethylsiloxane
  • the polyalkylarylsiloxanes are particularly chosen from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes with a viscosity ranging from 1 xW 5 to 5x1 O’ 2 m 2 /s at 25°C.
  • oils of the SF series from General Electric such as SF 1023, SF 1154, SF 1250 and SF 1265.
  • non-amino silicones that are more particularly preferred according to the invention are polydimethylsiloxanes containing trimethylsilyl end groups (CTFA: dimethicone).
  • CTFA trimethylsilyl end groups
  • the composition according to the invention may comprise one or more amino silicones.
  • amino silicone denotes any silicone including at least one primary, secondary or tertiary amine or a quaternary ammonium group.
  • the amino silicones that may be used according to the present invention may be volatile or non-volatile and cyclic, linear or branched, and preferably have a viscosity ranging from 5 x w 6 to 2.5 m 2 /s at 25°C, for example from 1 x w 5 to 1 m 2 /s.
  • amino silicone(s) are chosen, alone or as mixtures, from the following compounds:
  • - G which is identical or different, denotes a hydrogen atom or a phenyl, OH, Ci-Cs alkyl, for example methyl, or Ci-Cs alkoxy, for example methoxy, group;
  • - a and a’ which may be identical or different, denote 0 or an integer from 1 to 3, in particular 0, with the proviso that at least one from among a and a’ is equal to zero,
  • - b denotes 0 or 1 , in particular 1 ,
  • n + m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and notably from 49 to 149, and m possibly denoting a number from 1 to 2000 and notably from 1 to 10; and
  • R’ which may be identical or different, denotes a monovalent radical of formula - C q H2qL in which q is a number ranging from 2 to 8 and L is an optionally quaternized amino group chosen from the following groups: -NR”-Q-N(R”)2, -N(R”)2, -N + (R”)3 A- , -N + H(R”) 2 A -N + H 2 (R”) A -NR”-Q-N + (R”)H 2 A; -NR”-Q-N + (R”) 2 H A’ and -NR”-Q- N + (R”)3 A in which R”, which may be identical or different, denotes hydrogen, phenyl, benzyl or a saturated monovalent hydrocarbon-based radical, for example a C1-C20 alkyl radical; Q denotes a linear or branched group of formula CrH2r, r being an integer ranging from 2 to 6, preferably from 2 to 4; and A’ represents a
  • amino silicones of formula (II) may be chosen from:
  • n + m and n are numbers such that the sum (n + m) ranges from 1 to 1000, notably from 50 to 250 and more particularly from 100 to 200; n denoting a number from 0 to 999 and notably from 49 to 249 and more particularly from 125 to 175, and m denoting a number from 1 to 1000, notably from 1 to 10 and more particularly from 1 to 5; and
  • R2 and R3 which may be identical or different, represent a hydroxyl or C1-C4 alkoxy radical, at least one of the radicals R1 to R3 denoting an alkoxy radical.
  • the alkoxy radical is a methoxy radical.
  • the hydroxy/alkoxy mole ratio preferably ranges from 0.2:1 to 0.4:1 and preferably from 0.25:1 to 0.35:1 and more particularly is equal to 0.3:1.
  • the weight-average molecular mass (Mw) of these silicones preferably ranges from 2000 to 1 000 000 g/mol and more particularly from 3500 to 200 000 g/mol.
  • - p and q are numbers such that the sum (p + q) ranges from 1 to 1000, in particular from 50 to 350 and more particularly from 150 to 250; p denoting a number from 0 to 999, notably from 49 to 349 and more particularly from 159 to 239, and q denoting a number from 1 to 1000, notably from 1 to 10 and more particularly from 1 to 5; and
  • - Ri and R2 which are different, represent a hydroxyl or C1-C4 alkoxy radical, at least one of the radicals R1 or R2 denoting an alkoxy radical.
  • the alkoxy radical is a methoxy radical.
  • the hydroxy/alkoxy mole ratio generally ranges from 1 :0.8 to 1 :1.1 and preferably from 1 :0.9 to 1 : 1 and more particularly is equal to 1 :0.95.
  • the weight-average molecular mass (Mw) of the silicone preferably ranges from 2000 to 200 000 g/mol, more preferentially from 5000 to 100 000 g/mol and in particular from 10 000 to 50 000 g/mol.
  • the commercial products comprising silicones of structure (IV) or (V) may include in their composition one or more other amino silicones, the structure of which is different from formula (IV) or (V).
  • a product containing amino silicones of structure (IV) is sold by the company Wacker under the name Belsil® ADM 652.
  • a product containing amino silicones of structure (V) is sold by Wacker under the name Fluid WR 1300®.
  • Another product containing amino silicones of structure (XIV) is sold by Wacker under the name Belsil ADM LOG 1®.
  • one particularly advantageous embodiment consists in using them in the form of an oil-in-water emulsion.
  • the oil-in-water emulsion may comprise one or more surfactants.
  • the surfactants may be of any nature but are preferably cationic and/or nonionic.
  • the number-average size of the silicone particles in the emulsion generally ranges from 3 nm to 500 nm.
  • n + m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and notably from 50 to 150, n denoting a number from 0 to 1999 and notably from 49 to 149, and m denoting a number from 1 to 2000 and notably from 1 to 10; and
  • A denotes a linear or branched alkylene radical containing from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably linear.
  • the weight-average molecular mass (Mw) of these amino silicones preferably ranges from 2000 to 1 000 000 g/mol and more particularly from 3500 to 200 000 g/mol.
  • a silicone corresponding to this formula is, for example, Xiameter MEM 8299 Emulsion from Dow Corning.
  • n + m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and notably from 49 to 149, and m possibly denoting a number from 1 to 2000 and notably from 1 to 10; and
  • A denotes a linear or branched alkylene radical containing from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably branched.
  • the weight-average molecular mass (Mw) of these amino silicones preferably ranges from 500 to 1 000 000 g/mol and more particularly from 1000 to 200 000 g/mol.
  • a silicone corresponding to this formula is, for example, DC2-8566 Amino Fluid from Dow Corning;
  • - Rs represents a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a C1-C18 alkyl or C2-C18 alkenyl radical, for example methyl;
  • - Re represents a divalent hydrocarbon-based radical, notably a C1-C18 alkylene radical or a divalent C1-C18, for example Ci-Cs, alkyleneoxy radical linked to the Si via an SiC bond;
  • - Q’ is an anion such as a halide ion, notably chloride, or an organic acid salt, notably acetate;
  • - r represents a mean statistical value ranging from 2 to 20 and in particular from 2 to 8;
  • - s represents a mean statistical value ranging from 20 to 200 and in particular from 20 to 50.
  • R7 which may be identical or different, represent a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a C1-C18 alkyl radical, a C2-C18 alkenyl radical or a ring comprising 5 or 6 carbon atoms, for example methyl;
  • - Re represents a divalent hydrocarbon-based radical, notably a C1-C18 alkylene radical or a divalent C1-C18, for example Ci-Cs, alkyleneoxy radical linked to the Si via an SiC bond;
  • - Rs which may be identical or different, represent a hydrogen atom, a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a C1-C18 alkyl radical, a C2-C18 alkenyl radical or a radical -R6-NHCOR7;
  • - X’ is an anion such as a halide ion, notably chloride, or an organic acid salt, notably acetate;
  • - r represents a mean statistical value ranging from 2 to 200 and in particular from 5 to 100.
  • silicones are for example described in patent application EP-A-0 530 974; mention may in particular be made of the silicone having the INCI name: Quaternium 80.
  • Silicones falling within this category are the silicones sold by the company Goldschmidt under the names Abil Quat 3270, Abil Quat 3272 and Abil Quat 3474;
  • R2 which may be identical or different, denote a C1-C4 alkyl radical or a phenyl group
  • - n is an integer ranging from 1 to 5
  • - m is an integer ranging from 1 to 5
  • - x is chosen such that the amine number ranges from 0.01 to 1 meq/g;
  • Said silicones are preferably formed from repeating units having the following general formulae:
  • - a is an integer greater than or equal to 1 , preferably ranging from 5 to 200 and more particularly ranging from 10 to 100;
  • - b is an integer between 0 and 200, preferably ranging from 4 to 100 and more particularly between 5 and 30;
  • - x is an integer ranging from 1 to 10 000 and more particularly from 10 to 5000;
  • - R is a hydrogen atom or a methyl
  • R which may be identical or different, represent a linear or branched divalent C2- C12 hydrocarbon-based radical, optionally including one or more heteroatoms such as oxygen; preferably, R, which may be identical or different, denote an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical or a CH2CH2CH2OCH2CH(OH)CH2- radical; preferentially, R denote a CH2CH2CH2OCH 2 CH(OH)CH2- radical; and
  • R’ which may be identical or different, represent a linear or branched divalent C2- C12 hydrocarbon-based radical, optionally including one or more heteroatoms such as oxygen; preferably, R’, which may be identical or different, denote an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical or a CH2CH2CH2OCH2CH(OH)CH2- radical; preferentially, R’ denote -CH(CH3)- CH2-.
  • the siloxane blocks preferably represent between 50 mol% and 95 mol% of the total weight of the silicone, more particularly from 70 mol% to 85 mol%.
  • the amine content is preferably between 0.02 and 0.5 meq/g of copolymer in a 30% solution in dipropylene glycol, more particularly between 0.05 and 0.2.
  • the weight-average molecular mass (Mw) of the silicone is preferably between 5000 and 1 000 000 g/mol and more particularly between 10 000 and 200 000 g/mol.
  • R R, R’ and R, which may be identical or different, denote a C1-C4 alkyl group or a hydroxyl group,
  • - x and y are numbers ranging from 1 to 5000; preferably, x ranges from 10 to 2000 and more preferentially from 100 to 1000; preferably, y ranges from 1 to 100;
  • Ri and R2 which may be identical or different, preferably identical, denote a linear or branched, saturated or unsaturated alkyl group comprising from 6 to 30 carbon atoms, preferably from 8 to 24 carbon atoms and more preferentially from 12 to 20 carbon atoms; and
  • - A denotes a linear or branched alkylene radical containing from 2 to 8 carbon atoms.
  • A comprises from 3 to 6 carbon atoms, more preferentially 4 carbon atoms; preferably, A is branched. Mention may be made in particular of the following divalent groups: -CH2CH2CH2- and -CH2CH(CH3)CH2-.
  • R1 and R2 are independent saturated linear alkyl groups comprising 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms and in particular from 12 to 20 carbon atoms; mention may be made in particular of dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups; and preferentially, R1 and R2, which may be identical or different, are chosen from hexadecyl (cetyl) and octadecyl (stearyl) groups.
  • - x ranges from 10 to 2000 and in particular from 100 to 1000;
  • - A comprises from 3 to 6 carbon atoms and notably 4 carbon atoms; preferably, A is branched; more particularly, A is chosen from the following divalent groups: - CH2CH2CH2 and -CH 2 CH(CH3)CH2-; and
  • R1 and R2 independently are saturated linear alkyl groups comprising from 6 to 30 carbon atoms, preferably from 8 to 24 carbon atoms and in particular from 12 to 20 carbon atoms; notably chosen from dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups; preferentially, R1 and R2, which may be identical or different, are chosen from hexadecyl (cetyl) and octadecyl (stearyl) groups.
  • a silicone of formula (XII) that is preferred is bis-cetearyl amodimethicone. Mention may be made in particular of the amino silicone sold under the name Silsoft AX by Momentive. H) polysiloxanes and notably polydimethylsiloxanes, including primary amine groups at only one chain end or on side chains, such as those of formula (XIV), (XV)
  • n and m are such that the weight-average molecular mass of the amino silicone is between 1000 and 55 000.
  • amino silicones of formula (XIV) mention may be made of the products sold under the names AMS-132, AMS-152, AMS-162, AMS-163, AMS-191 and AMS-1203 by the company Gelest and KF-8015 by the company Shin-Etsu.
  • n is such that the weight-average molecular mass of the amino silicone is between 500 and 3000.
  • amino silicones of formula (XV) mention may be made of the products sold under the names MCR-A11 and MCR-A12 by the company Gelest.
  • n and m are such that the weight-average molecular mass of the amino silicone is between 500 and 50 000.
  • amino silicones of formula (XVI) mention may be made of the aminopropyl phenyl trimethicone sold under the name DC 2-2078 Fluid by the company Dow Coming.
  • the cosmetic composition according to the invention may also comprise, as silicone, an amino silicone corresponding to formula (XVIII) below: in which:
  • - n is a number between 1 and 1000, preferably between 10 and 500, better still between 25 and 100, even better still between 50 and 80;
  • - m is a number between 1 and 200, preferably between 1 and 100, better still between 1 and 10 and even better still between 1 and 5;
  • R’ which may be identical or different, preferably identical, are saturated or unsaturated, linear or branched, alkyl radicals comprising from 8 to 30 carbon atoms, preferably from 10 to 24 carbon atoms, notably from 12 to 18 carbon atoms; it being possible for said radicals optionally to be substituted with one or more hydroxyl OH groups;
  • - R’ is a linear or branched divalent alkylene radical containing from 1 to 6 carbon atoms, notably from 2 to 5 carbon atoms;
  • - R is a linear or branched divalent alkylene radical containing from 1 to 6 carbon atoms, notably from 1 to 5 carbon atoms.
  • the radicals R’ which may be identical or different, are saturated linear alkyl radicals comprising from 8 to 30 carbon atoms, preferably from 10 to 24 carbon atoms, notably from 12 to 18 carbon atoms; mention may be made in particular of dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl radicals; preferentially, the radicals R’”, which may be identical or different, are chosen from saturated linear alkyl radicals containing from 12 to 16 carbon atoms, which are notably C13, C14 or C15 radicals, alone or as a mixture, and better still represent a mixture of C13, C14 and C15 radicals.
  • radicals R’ are identical.
  • R' is a linear or branched, preferably branched, divalent alkylene radical comprising from 1 to 6 carbon atoms, notably from 2 to 5 carbon atoms; notably a - CH2-CH2-CH2-, -CH2-CH(CH 3 )-CH2- or -CH2-CH 2 -CH(CH 3 )- radical.
  • R is a linear divalent alkylene radical comprising from 1 to 6 carbon atoms, notably from 1 to 4 carbon atoms, in particular a -CH2-CH2- radical.
  • the composition may comprise one or more silicones of formula (XVIII) in which:
  • - n is a number between 50 and 80;
  • - m is a number between 1 and 5;
  • - R’ is a divalent alkylene radical having from 2 to 5 carbon atoms
  • - R is a linear divalent alkylene radical having from 1 to 4 carbon atoms.
  • composition may comprise one or more silicones of formula (XVIII) in which:
  • - n is a number between 50 and 80;
  • - m is a number between 1 and 5;
  • - R’ is a -(CH 2 )3-, -CH2-CH(CH 3 )-CH2- or -CH2-CH2-CH(CH 3 )- radical, and
  • - R is a -(CH2)2- radical.
  • a most particularly preferred silicone of formula (XVIII) is Bis(C13-15 Alkoxy) PG- Amodimethicone (INCI name). Mention may notably be made of the silicone sold under the name Dowsil 8500 Conditioning Agent by Dow.
  • amino silicone(s) are chosen, alone or as a mixture, from:
  • the composition according to the present invention may comprise the silicone(s) in a total content preferably ranging from 0.3% to 5% by weight, better still from 0.4% to 4% by weight, preferentially from 0.6% to 3% by weight and more preferentially from 0.7% to 2.5% by weight, relative to the total weight of the composition.
  • composition according to the present invention may comprise the amino silicone(s) in a total content preferably ranging from 0.3% to 5% by weight, better still from 0.4% to 4% by weight, preferentially from 0.6% to 3% by weight and better still from 0.7% to 2.5% by weight, relative to the total weight of the composition.
  • Cationic surfactants preferably ranging from 0.3% to 5% by weight, better still from 0.4% to 4% by weight, preferentially from 0.6% to 3% by weight and better still from 0.7% to 2.5% by weight, relative to the total weight of the composition.
  • composition used according to the invention may optionally comprise one or more cationic surfactants.
  • Said cationic surfactants are non-silicone surfactants, that is to say that they do not contain an Si-0 group.
  • They are preferably chosen from primary, secondary or tertiary fatty amines, which are optionally polyoxyalkylenated, or salts thereof, and quaternary ammonium salts, and mixtures thereof.
  • composition can comprise one or more cationic surfactants chosen, alone or as a mixture, from the following compounds, which are quaternary ammonium salts:
  • X’ is an anion notably chosen from the group of halides, phosphates, acetates, lactates, (Ci-C4)alkyl sulfates, (Ci-C4)alkylsulfonates or (Ci-C4)alkylarylsulfonates;
  • the groups Ri to R4 which may be identical or different, represent a linear or branched aliphatic group including from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, at least one of the groups R1 to R4 denoting a linear or branched aliphatic group including from 8 to 30 carbon atoms, preferably from 12 to 24 carbon atoms.
  • the aliphatic groups may include heteroatoms notably such as oxygen, nitrogen, sulfur and halogens.
  • the aliphatic groups are chosen, for example, from C1-C30 alkyl, C1-C30 alkoxy, (C2-C6) polyoxyalkylene, C1-C30 alkylamide, (C12- C22)alkylamido(C2-C6)alkyl, (Ci2-C22)alkyl acetate, and C1-C30 hydroxyalkyl groups.
  • tetraalkylammonium salts for instance dialkyldimethylammonium or alkyltrimethylammonium salts in which the alkyl group includes from about 12 to 22 carbon atoms, in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium or benzyldimethylstearylammonium salts, and also palmitylamidopropyltrimethylammonium salts, stearamidopropyltrimethylammonium salts, stearamidopropyldimethylcetearylammonium salts, or stearamidopropyldimethyl(myristyl acetate)ammonium salts such as those sold under the name Ceraphyl® 70 by the company Van Dyk.
  • X is an anion chosen from the group of halides, phosphates, acetates, lactates, alkyl sulfates, alkyl- or alkylaryl-sulfonates in which the alkyl and aryl groups preferably comprise, respectively, from 1 to 20 carbon atoms and from 6 to 30 carbon atoms.
  • Rs and Re denote a mixture of alkenyl or alkyl groups including from 12 to 21 carbon atoms, for example derived from tallow fatty acids, R7 denotes a methyl group and Rs denotes a hydrogen atom.
  • Such a product is sold, for example, under the name Rewoquat® W 75 by the company Rewo,
  • R9 denotes an alkyl radical including from about 16 to 30 carbon atoms which is optionally hydroxylated and/or optionally interrupted with one or more oxygen atoms,
  • R10 is chosen from hydrogen or an alkyl radical including from 1 to 4 carbon atoms or a group (R9a)(Rioa)(Rna)N-(CH2)3, with Rg a , Rioa, Rua, R11 , R12, R13 and R14, which may be identical or different, chosen from hydrogen or an alkyl radical including from 1 to 4 carbon atoms, and
  • X’ is an anion chosen from the group of halides, acetates, phosphates, nitrates, (C1- C4)alkyl sulfates, (Ci-C4)alkylsulfonates and (Ci-C4)alkylarylsulfonates, in particular methyl sulfate and ethyl sulfate.
  • Such compounds are, for example, Finquat CT-P, sold by Finetex (Quaternium 89), and Finquat CT, sold by Finetex (Quaternium 75); - quaternary ammonium salts containing at least one ester function, such as those of formula (V) below: in which:
  • Rw is chosen from Ci-Ce alkyl groups and Ci-Ce hydroxyalkyl or dihydroxyalkyl groups;
  • Rw is chosen from the group R19-C(O)-; groups R20 which are linear or branched, saturated or unsaturated C1-C22 hydrocarbon-based groups; a hydrogen atom;
  • Rw is chosen from the group R21 -C(O)-; groups R22 which are linear or branched, saturated or unsaturated Ci-Ce hydrocarbon-based groups; a hydrogen atom;
  • R17, R19 and R21 which may be identical or different, are chosen from linear or branched, saturated or unsaturated C7-C21 hydrocarbon-based groups; r, s and t, which may be identical or different, are integers having values from 2 to 6; y is an integer ranging from 1 to 10; x and z, which may be identical or different, are integers having a value from 0 to 10;
  • X is a simple or complex, organic or mineral anion; with the proviso that the sum x + y + z is from 1 to 15, that when x is 0 then Rw denotes R20, and that when z is 0 then R denotes R22.
  • the alkyl groups Rw may be linear or branched, and more particularly linear.
  • Rw denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group.
  • the sum x + y + z is from 1 to 10.
  • Rw is a hydrocarbon-based group R20, it may be long and contain from 12 to 22 carbon atoms, or may be short and contain from 1 to 3 carbon atoms.
  • Rw is a hydrocarbon-based group R22, it preferably contains 1 to 3 carbon atoms.
  • R17, R19 and R21 which may be identical or different, are chosen from linear or branched, saturated or unsaturated C11-C21 hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated C11- C21 alkyl and alkenyl groups.
  • x and z which may be identical or different, are equal to 0 or 1 .
  • y is equal to 1 .
  • r, s and t which may be identical or different, are equal to 2 or 3, and even more particularly are equal to 2.
  • the anion X’ is preferably a halide (chloride, bromide or iodide) or an alkyl sulfate, more particularly methyl sulfate.
  • a halide chloride, bromide or iodide
  • alkyl sulfate more particularly methyl sulfate.
  • use may be made of methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion that is compatible with the ammonium bearing an ester function.
  • the anion X’ is even more particularly chloride or methyl sulfate.
  • composition according to the invention use may be made more particularly of the ammonium salts of formula (V) in which R15 denotes a methyl or ethyl group, x and y are equal to 1 ; z is equal to 0 or 1 ; r, s and t are equal to 2;
  • R17, R19 and R21 which may be identical or different, are chosen from linear or branched, saturated or unsaturated C13-C17 hydrocarbon-based groups, and preferably from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl groups.
  • the hydrocarbon-based groups are linear.
  • acyl groups preferably contain 14 to 18 carbon atoms and are derived more particularly from a plant oil such as palm oil or sunflower oil. When the compound contains several acyl groups, these groups may be identical or different.
  • These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, an alkyldiethanolamine or an alkyldiisopropanolamine, which are optionally oxyalkylenated, with C10-C30 fatty acids or with mixtures of C10-C30 fatty acids of plant or animal origin, or by transesterification of the methyl esters thereof.
  • This esterification is followed by a quaternization using an alkylating agent such as an alkyl halide (preferably a methyl or ethyl halide), a dialkyl sulfate (preferably a methyl or ethyl sulfate), methyl methanesulfonate, methyl paratoluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.
  • an alkylating agent such as an alkyl halide (preferably a methyl or ethyl halide), a dialkyl sulfate (preferably a methyl or ethyl sulfate), methyl methanesulfonate, methyl paratoluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.
  • Such compounds are sold, for example, under the names Dehyquart® by the company Henkel, Stepanquat® by the company Stepan, Noxamium® by the company CECA or Rewoquat® WE 18 by the company Rewo-Witco.
  • composition according to the invention may contain, for example, a mixture of quaternary ammonium monoester, diester and triester salts with a weight majority of diester salts.
  • ammonium salts containing at least one ester function that are described in patents US-A-4 874 554 and US-A-4 137 180.
  • ammonium salts containing at least one ester function contain two ester functions.
  • quaternary ammonium salts containing at least one ester function that may be used, it is preferred to use dipalmitoylethylhydroxyethylmethylammonium salts.
  • fatty amine means a compound comprising at least one optionally (poly)oxyalkylenated primary, secondary or tertiary amine function, or salts thereof and comprising at least one C6-C30 and preferably Cs-Cso hydrocarbon-based chain.
  • the fatty amines of use according to the invention are not (poly)oxyalkylenated.
  • Fatty amines that may be mentioned include amidoamines.
  • the amidoamines according to the invention may be chosen from fatty amidoamines, it being possible for the fatty chain to be borne by the amine group or by the amido group.
  • amidoamine means a compound comprising at least one amide function and at least one primary, secondary or tertiary amine function.
  • fatty amidoamine means an amidoamine comprising, in general, at least one Ce-Cso hydrocarbon-based chain.
  • the fatty amidoamines of use according to the invention are not quaternized.
  • the fatty amidoamines of use according to the invention are not (poly)oxyalkylenated.
  • - R represents a substituted or unsubstituted, linear or branched, saturated or unsaturated monovalent hydrocarbon-based radical containing from 5 to 29 carbon atoms, preferably from 7 to 23 carbon atoms, and in particular a linear or branched C5-C29 and preferably C7-C23 alkyl radical, or a linear or branched C5-C29 and preferably C7-C23 alkenyl radical;
  • - R represents a divalent hydrocarbon-based radical containing less than 6 carbon atoms, preferably from 2 to 4 carbon atoms and better still 3 carbon atoms;
  • R’ which may be identical or different, represent a substituted or unsubstituted, saturated or unsaturated, linear or branched, monovalent hydrocarbon-based radical containing less than 6 carbon atoms, preferably from 1 to 4 carbon atoms, preferably a methyl radical.
  • the fatty amidoamines of formula (VI) are chosen, for example, from oleamidopropyldimethylamine, stearamidopropyldimethylamine, notably the product sold by the company Index Chemical Company under the name Lexamine S13, isostearamidopropyldimethylamine, stearamidoethyldimethylamine, lauramidopropyldimethylamine, myristamidopropyldimethylamine, behenamidopropyldimethylamine, dilinoleamidopropyldimethylamine, palmitamidopropyldimethylamine, ricinoleamindopropyldimethylamine soyamidopropyldimethylamine, avocadoamidopropyldimethylamine cocamidopropyldimethylamine, minkamidopropyldimethylamine oatamidopropyldimethylamine, sesamidopropyldimethylamine tallamidoprop
  • the fatty amidoamines are chosen from oleamidopropyldimethylamine, stearamidopropyldimethylamine, brassicamidopropyldimethylamine and mixtures thereof.
  • the cationic surfactant(s) are preferably chosen from those of formula (II) above, those of formula (V) above, those of formula (VI) above, and mixtures thereof; better still from those of formula (II) above, those of formula (VI) above, and mixtures thereof; even better still from those of formula (II) above.
  • the cationic surfactant(s) may be chosen from salts such as chlorides, bromides or methosulfates, of tetraalkylammonium, for instance dialkyldimethylammonium or alkyltrimethylammonium salts in which the alkyl group includes from about 12 to 22 carbon atoms, in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium or benzyldimethylstearylammonium salts; dipalmitoylethylhydroxyethylmethylammonium salts such as dipalmitoylethylhydroxyethylmethylammonium methosulfate; and mixtures thereof. Even more preferentially, they are chosen from cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, dipalmitoylethylhydroxyethylmethylammonium methosulfate, and mixtures thereof.
  • the total content of cationic surfactant(s) in the composition according to the invention preferably ranges from 0.1 % to 10% by weight, notably from 0.2% to 8% by weight, better still from 0.3% to 7% by weight, even better still from 0.5% to 5% by weight, relative to the total weight of the composition.
  • the ratio by weight of the total content of cationic surfactant(s) to the total content of compounds of amino acid type is greater than or equal to 1 .
  • composition used according to the invention may optionally comprise one or more cationic polymers other than the associative polymers described above. This or these cationic polymer(s) are therefore non-associative.
  • cationic polymer denotes any non-silicone (not comprising any silicon atoms) polymer containing cationic groups and/or groups that can be ionized into cationic groups and not containing any anionic groups and/or groups that can be ionized into anionic groups.
  • the cationic polymers that may be employed preferably have a cationic charge density of less than or equal to 5 milliequivalents/gram (meq/g), better still of less than or equal to 4 meq/g.
  • the cationic charge density of a polymer corresponds to the number of moles of cationic charges per unit mass of polymer under the conditions where the latter is completely ionized. It may be determined by calculation if the structure of the polymer is known, i.e. the structure of the monomers constituting the polymer and their molar proportion or weight proportion. It may also be determined experimentally by the Kjeldahl method.
  • the cationic polymers that may be used preferably have a weight-average molar mass (Mw) of between 500 and 5x10 6 approximately and preferably between 10 3 and 3x10 6 approximately.
  • the cationic polymers that may be employed are preferably non-associative.
  • R3 which may be identical or different, denote a hydrogen atom or a CH3 radical
  • - A which may be identical or different, represent a linear or branched divalent alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or a hydroxyalkyl group of 1 to 4 carbon atoms;
  • R4 R4, Rs and Re, which may be identical or different, represent an alkyl group containing from 1 to 18 carbon atoms or a benzyl radical, preferably an alkyl group containing from 1 to 6 carbon atoms;
  • R1 and R2 which may be identical or different, represent a hydrogen atom or an alkyl group containing from 1 to 6 carbon atoms, preferably methyl or ethyl;
  • - X denotes an anion derived from a mineral or organic acid, such as a methosulfate anion or a halide such as chloride or bromide.
  • the copolymers of family (1 ) may also contain one or more units derived from comonomers that may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (C1 -C4) alkyls, acrylic or methacrylic acid esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.
  • crosslinked polymers of methacryloyloxy(C1 -C4)alkyltri(C1 - C4)alkylammonium salts such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homopolymerization or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylenebisacrylamide.
  • Use may be made more particularly of a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion comprising 50% by weight of said copolymer in mineral oil.
  • This dispersion is sold under the name Salcare® SC 92 by the company Ciba.
  • Use may also be made of a crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymer comprising approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are sold under the names Salcare® SC 95 and Salcare® SC 96 by the company Ciba.
  • cationic polysaccharides notably cationic celluloses and galactomannan gums.
  • cationic polysaccharides mention may be made more particularly of cellulose ether derivatives including quaternary ammonium groups, cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and cationic galactomannan gums.
  • cellulose ether derivatives including quaternary ammonium groups are notably described in FR 1 492 597; they are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose that has reacted with an epoxide substituted with a trimethylammonium group.
  • Cationic cellulose copolymers and cellulose derivatives grafted with a water-soluble quaternary ammonium monomer are described notably in patent US 4 131 576; mention may be made of hydroxyalkyl celluloses, for instance hydroxymethyl, hydroxyethyl or hydroxypropyl celluloses notably grafted with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.
  • a particularly preferred cationic cellulose that may notably be mentioned is the polymer having the INCI name Polyquaternium-10.
  • cationic galactomannan gums are notably described in patents US 3 589 578 and US 4 031 307; mention may be made of cationic guar gums, notably those comprising cationic trialkylammonium groups, notably trimethylammonium. Mention may thus be made of guar gums modified with a 2,3- epoxypropyltrimethylammonium salt (for example a chloride).
  • guar gums Preferably, 2% to 30% by number of the hydroxyl functions of the guar gums bear cationic trialkylammonium groups. Even more preferentially, 5% to 20% by number of the hydroxyl functions of these guar gums are branched with cationic trialkylammonium groups. Among these trialkylammonium groups, mention may most particularly be made of the trimethylammonium and triethylammonium groups. Even more preferentially, these groups represent from 5% to 20% by weight relative to the total weight of the modified guar gum. According to the invention, guar gums modified with 2,3-epoxypropyltrimethylammonium chloride may be used.
  • polyaminoamide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional agents Mention may be made, for example, of adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl radical includes from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl.
  • the alkyl radical includes from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl.
  • Polymers of this type are sold in particular under the name Hercosett 57 by the company Hercules Inc. or under the name PD 170 or Delsette 101 by the company Hercules in the case of the adipic acid/epoxy-propyl/diethylenetriamine copolymer.
  • cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium such as the homopolymers or copolymers including, as main constituent of the chain, units corresponding to formula (I) or (II): in which
  • R12 denotes a hydrogen atom or a methyl radical
  • R10 and R11 independently of each other, denote a Ci-Ce alkyl group, a C1-C5 hydroxyalkyl group, a C1-C4 amidoalkyl group; or alternatively R10 and R11 may denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidinyl or morpholinyl; R10 and R11 , independently of each other, preferably denote a C1-C4 alkyl group;
  • - Y’ is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate.
  • R13, R14, RIS and Rie which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms or C1-C12 hydroxyalkyl aliphatic radicals; or else R13, R14, R15 and R16, together or separately, form, with the nitrogen atoms to which they are attached, heterocycles optionally comprising a second nonnitrogen heteroatom; or else R13, R14, R15 and R16 represent a linear or branched Ci-Ce alkyl radical substituted with a nitrile, ester, acyl, amide or -CO-O-R17-D or -CO-NH-R17-D group, where R17 is an alkylene and D is a quaternary ammonium group;
  • A1 and B1 represent linear or branched, saturated or unsaturated, divalent polymethylene groups comprising from 2 to 20 carbon atoms, which may contain, linked to or intercalated in the main chain, one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and
  • - X denotes an anion derived from a mineral or organic acid; it being understood that A1, R13 and R15 can form, with the two nitrogen atoms to which they are attached, a piperazine ring; in addition, if A1 denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 may also denote a group (CH2)n-CO-D-OC-(CH2)p- with n and p, which may be identical or different, being integers ranging from 2 to 20, and D denoting: a) a glycol residue of formula -O-Z-O-, in which Z denotes a linear or branched hydrocarbon-based radical or a group corresponding to one of the following formulae: -(CH2CH2O)x-CH2CH2- and -[CH2CH(CH3)O]y-CH2CH(CH3)- , in which x and y denote an integer from 1 to 4, representing a defined and unique degree
  • X’ is an anion, such as chloride or bromide.
  • Mn number-average molar mass
  • R1 , R2, R3 and R4 which may be identical or different, denote an alkyl or hydroxyalkyl radical containing from 1 to 4 carbon atoms, n and p are integers ranging from 2 to 20, and X- is an anion derived from a mineral or organic acid.
  • (9) polyquaternary ammonium polymers comprising units of formula (V): in which:
  • R - R , R19, R20 and R21 which may be identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, [3-hydroxyethyl, [3-hydroxypropyl or - CH2CH2(OCH2CH2) P OH radical, in which p is equal to 0 or to an integer between 1 and 6, with the proviso that R , R19, R20 and R21 do not simultaneously represent a hydrogen atom,
  • - r and s which may be identical or different, are integers between 1 and 6,
  • - X denotes an anion such as a halide
  • - A denotes a divalent dihalide radical or preferably represents -CH2-CH2-O-CH2- CH2-.
  • Examples that may be mentioned include the products Mirapol® A 15, Mirapol® AD1 , Mirapol® AZ1 and Mirapol® 175 sold by the company Miranol.
  • polyamines such as Polyquart® H sold by Cognis, which is referenced under the name Polyethylene Glycol (15) Tallow Polyamine in the CTFA dictionary;
  • these polymers may be notably chosen from homopolymers or copolymers including one or more units derived from vinylamine and optionally one or more units derived from vinylformamide.
  • these cationic polymers are chosen from polymers including, in their structure, from 5 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 95 mol% of units corresponding to formula (B), preferentially from 10 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 90 mol% of units corresponding to formula (B).
  • These polymers may be obtained, for example, by partial hydrolysis of polyvinylformamide. This hydrolysis may take place in acidic or basic medium.
  • the weight-average molecular mass of said polymer measured by light scattering, may range from 1000 to 3 000 000 g/mol, preferably from 10 000 to 1 000 000 and more particularly from 100 000 to 500 000 g/mol.
  • the polymers including units of formula (A) and optionally units of formula (B) are notably sold under the name Lupamin by the company BASF, for instance, in a nonlimiting manner, the products sold under the names Lupamin 9095, Lupamin 5095, Lupamin 1095, Lupamin 9030 (or Luviquat 9030) and Lupamin 9010.
  • the cationic polymers that may be employed in the context of the invention are chosen, alone or as a mixture, from the polymers of family (1 ) and cationic polysaccharides, notably cationic celluloses, such as Polyquaternium-10; cationic galactomannan gums, notably cationic guar gums; and also mixtures thereof.
  • the composition according to the invention may comprise the cationic polymer(s) in a total amount ranging from 0.01 % to 10% by weight, better still from 0.05% to 5% by weight, even better still from 0.1 % to 2% by weight, relative to the total weight of the composition.
  • the composition according to the invention may comprise the cationic polysaccharide(s) in a total amount ranging from 0.01 % to 10% by weight, better still from 0.05% to 5% by weight, even better still from 0.1 % to 2% by weight, relative to the total weight of the composition.
  • composition used according to the invention may optionally comprise one or more nonionic polysaccharides other than the associative polymers described above. This or these nonionic polysaccharides are thus non-associative.
  • the nonionic polysaccharides are preferably chosen, alone or as a mixture, from celluloses, starches, galactomannans and their nonionic derivatives, notably their ethers or esters.
  • polymers may be physically or chemically modified. Mention may be made, as physical treatment, of the temperature and mention may be made, as chemical treatment, of esterification, etherification, amidation and oxidation reactions, in so far as these treatments make it possible to give polymers that are nonionic.
  • nonionic guar gums which can be modified with (poly)hydroxy(Ci-Ce)alkyl groups, notably hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.
  • These guar gums are well known from the prior art and may be prepared, for example, by reacting corresponding alkene oxides, for instance propylene oxides, with the guar gum so as to obtain a guar gum modified with hydroxypropyl groups.
  • the degree of hydroxyalkylation preferably ranges from 0.4 to 1 .2 and corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on the guar gum.
  • nonionic guar gums optionally modified with hydroxyalkyl groups are, for example, sold under the trade names Jaguar HP8, Jaguar HP60, Jaguar HP120, Jaguar HP105 SGI and Jaguar HP8 SGI by the company Rhodia Chimie.
  • the botanical origin of the starch molecules that may be used in the present invention may be cereals or tubers.
  • the starches are chosen, for example, from corn starch, rice starch, cassava starch, barley starch, potato starch, wheat starch, sorghum starch and pea starch.
  • the starches may be chemically or physically modified, notably by one or more of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation, heat treatments.
  • the starch molecules may be derived from any plant source of starch, in particular such as corn, potato, oat, rice, tapioca, sorghum, barley or wheat. It is also possible to use hydrolysates of the starches mentioned above.
  • the starch is preferably derived from potato.
  • the nonionic polysaccharides may also be cellulose-based polymers not including a C10-C30 fatty chain in their structure.
  • cellulose-based refers to any polysaccharide compound bearing in its structure sequences of glucose residues linked together by (3-1 ,4 bonds; the cellulose-based polymers may be unsubstituted celluloses, and/or derivatives of nonionic celluloses.
  • the cellulose-based polymers that may be used according to the invention may be chosen from unsubstituted celluloses, including those in a microcrystalline form, and cellulose ethers.
  • unsubstituted celluloses including those in a microcrystalline form
  • cellulose ethers include those in a microcrystalline form
  • cellulose ethers include those in a microcrystalline form
  • cellulose ethers include those in a microcrystalline form
  • cellulose ethers include those in a microcrystalline form
  • cellulose ethers include those in a microcrystalline form
  • cellulose ethers include those in a microcrystalline form
  • cellulose ethers include those in a microcrystalline form
  • cellulose ethers include those in a microcrystalline form
  • cellulose ethers include those in a microcrystalline form
  • cellulose ethers include those in a microcrystalline form
  • cellulose ethers include those in a microcrystalline form
  • cellulose ethers include those in a microcrystalline form
  • cellulose ethers include those in
  • nonionic cellulose ethers that may be mentioned are (C1- C4)alkylcelluloses, such as methylcelluloses and ethylcelluloses (for example Ethocel Standard 100 Premium from Dow Chemical); (poly)hydroxy(Ci- C4)alkylcelluloses, such as hydroxymethylcelluloses, hydroxyethylcelluloses (for example Natrosol 250 HHR sold by Aquaion) and hydroxypropylcelluloses (for example Klucel EF from Aquaion); mixed (poly)hydroxy(Ci-C4)alkyl(Ci- C4)alkylcelluloses, such as hydroxypropylmethylcelluloses (for example Methocel E4M from Dow Chemical), hydroxyethylmethylcelluloses, hydroxyethylethylcelluloses (for example Bermocoll E 481 FQ from Akzo Nobel) and hydroxybutylmethylcelluloses.
  • C1- C4alkylcelluloses such as methylcelluloses and ethylcelluloses (for example Eth
  • the nonionic polysaccharides are chosen, alone or as a mixture, from celluloses, galactomannans and their nonionic derivatives, notably their ethers; and better still, alone or as a mixture, from nonionic guar gums optionally modified with (poly)hydroxy(Ci-Ce)alkyl, in particular hydroxypropyl, groups; and/or celluloses, which are substituted or substituted, and cellulose ethers, such as (Ci- C4)alkylcelluloses and (poly)hydroxy(Ci-C4)alkylcelluloses.
  • the nonionic polysaccharides are chosen, alone or as a mixture, from nonionic guar gums optionally modified with (poly)hydroxy(Ci-Cs)alkyl, notably hydroxypropyl (INCI name: Hydroxypropyl Guar), groups.
  • the composition according to the invention may comprise the nonionic polysaccharide(s) in a total amount ranging from 0.01 % to 10% by weight, better still from 0.05% to 5% by weight, even better still from 0.1 % to 2% by weight, relative to the total weight of the composition.
  • the composition according to the invention may comprise the nonionic polysaccharide(s) chosen from celluloses, galactomannans and their nonionic derivatives, notably their ethers, and mixtures thereof, in a total amount ranging from 0.01 % to 10% by weight, better still from 0.05% to 5% by weight, even better still from 0.1 % to 2% by weight, relative to the total weight of the composition.
  • the composition according to the invention may comprise one or more cationic polymers and one or more nonionic polysaccharides; notably one or more cationic polysaccharides and one or more nonionic polysaccharides; better still one or more cationic polysaccharides chosen from cationic guar gums and cationic celluloses, and one or more nonionic guar gums.
  • composition used according to the invention may optionally comprise one or more nonionic surfactants.
  • nonionic surfactants examples include the following compounds, alone or as a mixture:
  • fatty acid esters of sucrose - optionally oxyalkylenated alkyl (poly)glycosides (0 to 10 oxyalkylene units) which may comprise from 1 to 15 glucose units;
  • the oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, preferably oxyethylene units.
  • the number of moles of ethylene oxide and/or propylene oxide preferably ranges from 1 to 250, more particularly from 2 to 100 and better still from 2 to 50; the number of moles of glycerol ranges notably from 1 to 50 and better still from 1 to 10.
  • nonionic surfactants according to the invention do not comprise any oxypropylene units.
  • they comprise a number of moles of ethylene oxide ranging from 1 to 250, notably from 2 to 100 and better still from 2 to 50.
  • glycerolated nonionic surfactants use is preferably made of monoglycerolated or polyglycerolated Cs to C40 alcohols, comprising from 1 to 50 mol of glycerol and preferably from 1 to 10 mol of glycerol.
  • lauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1.5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleyl/cetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.
  • glycerolated alcohols it is more particularly preferred to use the Cs to C10 alcohol containing 1 mol of glycerol, the C10 to C12 alcohol containing 1 mol of glycerol and the C12 alcohol containing 1 .5 mol of glycerol.
  • Nonionic surfactants of alkyl (poly)glycoside type may notably be represented by the following general formula: R1 O-(R2O)t-(G)v in which:
  • R1 represents a linear or branched alkyl or alkenyl radical including 6 to 24 carbon atoms and notably 8 to 18 carbon atoms, or an alkylphenyl radical of which the linear or branched alkyl radical includes 6 to 24 carbon atoms and notably 8 to 18 carbon atoms,
  • R2 represents an alkylene radical including 2 to 4 carbon atoms
  • - G represents a sugar unit including 5 to 6 carbon atoms
  • - 1 denotes a value ranging from 0 to 10 and preferably from 0 to 4;
  • - v denotes a value ranging from 1 to 15 and preferably from 1 to 4.
  • alkyl(poly)glycoside surfactants are compounds of the formula described above in which:
  • R1 denotes a linear or branched, saturated or unsaturated alkyl radical including from 8 to 18 carbon atoms
  • R2 represents an alkylene radical including 2 to 4 carbon atoms
  • - 1 denotes a value ranging from 0 to 3 and preferably equal to 0,
  • - G denotes glucose, fructose or galactose, preferably glucose
  • the degree of polymerization i.e. the value of v, to range from 1 to 15 and preferably from 1 to 4; the mean degree of polymerization more particularly being between 1 and 2.
  • the glucoside bonds between the sugar units are generally of 1 -6 or 1 -4 type and preferably of 1 -4 type.
  • the alkyl(poly)glycoside surfactant is an alkyl(poly)glucoside surfactant.
  • C8/C16 alkyl (poly)glycosides of 1 -4 type notably as an aqueous 53% solution, such as those sold by Cognis under the reference Plantacare® 818 UP.
  • nonionic surfactant(s) used in the composition according to the invention are preferentially chosen, alone or as a mixture, from:
  • - saturated or unsaturated, linear or branched, oxyethylenated Cs to C40 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 40 mol of ethylene oxide and preferably including one or two fatty chains;
  • - monoglycerolated or polyglycerolated Cs to C40 alcohols comprising from 1 to 50 mol of glycerol and preferably from 1 to 10 mol of glycerol;
  • the nonionic surfactant(s) used in the composition according to the invention are chosen, alone or as a mixture, from: - saturated or unsaturated, linear or branched, oxyethylenated Cs to C40 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 40 mol of ethylene oxide and including one or two fatty chains, notably at least one C8-C20, notably C10-C18, alkyl chain,
  • the composition according to the invention comprises the nonionic surfactant(s) in a total content ranging from 0.05% to 10% by weight, preferably from 0.1 % to 5% by weight, preferentially from 0.2% to 3% by weight, relative to the total weight of the composition according to the invention.
  • composition used according to the invention may optionally comprise one or more non-silicone fatty substances, which may be chosen from solid fatty substances, liquid fatty substances and mixtures thereof.
  • non-silicone fatty substance means a fatty substance not containing any Si-0 bonds.
  • solid fatty substance means a fatty substance having a melting point of greater than 25°C, preferably greater than or equal to 28°C, preferentially greater than or equal to 30°C, at atmospheric pressure (1.013 x 10 5 Pa).
  • the solid fatty substances that may be used in the present invention are neither (poly)oxyalkylenated nor (poly)glycerolated.
  • the solid fatty substances may be chosen from solid fatty acids, solid fatty alcohols, solid esters of fatty acids and/or of fatty alcohols, waxes and ceramides, and mixtures thereof.
  • fatty acid means a long-chain carboxylic acid comprising from 6 to 40 carbon atoms, preferably from 8 to 30 carbon atoms.
  • the solid fatty acids according to the invention preferentially comprise from 10 to 30 carbon atoms and better still from 14 to 22 carbon atoms. These fatty acids are neither oxyalkylenated nor glycerolated.
  • the solid fatty acids that may be used in the present invention are notably chosen from myristic acid, cetylic acid, stearylic acid, palmitic acid, stearic acid, lauric acid, behenic acid, and mixtures thereof. Said fatty acids are different from the (poly)hydroxylated carboxylic acids comprising from 2 to 8 carbon atoms described previously.
  • fatty alcohol means a long-chain aliphatic alcohol comprising from 6 to 40 carbon atoms, preferably from 8 to 30 carbon atoms, and comprising at least one hydroxyl group OH. These fatty alcohols are neither oxyalkylenated nor glycerolated.
  • the solid fatty alcohols may be saturated or unsaturated, and linear or branched, and include from 8 to 40 carbon atoms, preferably from 10 to 30 carbon atoms, better still from 12 to 30 carbon atoms.
  • the solid fatty alcohols have the structure R-OH with R denoting a linear alkyl group, optionally substituted with one or more hydroxyl groups, comprising from 8 to 40, preferentially from 10 to 30 carbon atoms, better still from 12 to 30, or even from 12 to 24 atoms and even better still from 14 to 22 carbon atoms.
  • the solid fatty alcohols that may be used are preferably chosen from saturated, and linear or branched, preferably linear and saturated, (mono)alcohols including from 8 to 40 carbon atoms, better still from 10 to 30, or even from 12 to 24 atoms and better still from 14 to 22 carbon atoms.
  • the solid fatty alcohols that may be used may be chosen, alone or as a mixture, from:
  • the solid fatty alcohol is chosen from cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, arachidyl alcohol, and mixtures thereof, such as cetylstearyl or cetearyl alcohol.
  • the solid fatty alcohol is chosen from cetyl alcohol, stearyl alcohol or their mixtures, such as cetylstearyl alcohol; better still, the solid fatty alcohol is cetylstearyl alcohol.
  • the solid esters of a fatty acid and/or of a fatty alcohol that may be used are preferably chosen from the esters resulting from C9-C26 fatty carboxylic acid and/or from C9-C26 fatty alcohol.
  • these solid fatty esters are esters of a linear or branched, saturated carboxylic acid including at least 10 carbon atoms, preferably from 10 to 30 carbon atoms and more particularly from 12 to 24 carbon atoms, and of a linear or branched, saturated monoalcohol, including at least 10 carbon atoms, preferably from 10 to 30 carbon atoms and more particularly from 12 to 24 carbon atoms.
  • the saturated carboxylic acids may optionally be hydroxylated, and are preferably monocarboxylic acids.
  • Esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1 -C22 alcohols and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of C2-C26 dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used.
  • the solid esters of a fatty acid and/or of a fatty alcohol are chosen from C9-C26 alkyl palmitates, notably myristyl, cetyl or stearyl palmitate; C9-C26 alkyl myristates, such as cetyl myristate, stearyl myristate and myristyl myristate; and C9- C26 alkyl stearates, notably myristyl, cetyl and stearyl stearate; and mixtures thereof.
  • the solid esters of a fatty acid and/or of a fatty alcohol are chosen from myristyl stearate, myristyl palmitate and mixtures thereof.
  • a wax is a lipophilic compound, which is solid at 25°C and atmospheric pressure, with a reversible solid/liquid change of state, having a melting point greater than about 40°C, which may be up to 200°C, and having in the solid state anisotropic crystal organization.
  • the size of the wax crystals is such that the crystals diffract and/or scatter light, giving the composition that comprises them a more or less opaque cloudy appearance.
  • the waxes that are suitable for use in the invention may be chosen from waxes of animal, plant or mineral origin, non-silicone synthetic waxes, and mixtures thereof.
  • hydrocarbon-based waxes for instance beeswax or modified beeswaxes (cera bellina), lanolin wax and lanolin derivatives, spermaceti; cork fiber or sugarcane waxes, olive tree
  • C20 to C60 microcrystalline waxes such as Microwax HW.
  • waxes obtained by catalytic hydrogenation of animal or plant oils containing linear or branched C8-C32 fatty chains may also be made of the waxes obtained by catalytic hydrogenation of animal or plant oils containing linear or branched C8-C32 fatty chains.
  • isomerized jojoba oil such as transisomerized partially hydrogenated jojoba oil, notably the product manufactured or sold by the company Desert Whale under the commercial reference Iso-Jojoba-50®, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut kernel oil, hydrogenated lanolin oil and bis(1 , 1 ,1 -trimethylolpropane) tetrastearate, notably the product sold under the name Hest 2T-4S® by the company Heterene.
  • the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol such as those sold under the names Phytowax Castor 16L64® and 22L73® by the company Sophim, may also be used.
  • a wax that may also be used is a C20 to C40 alkyl (hydroxystearyloxy)stearate (the alkyl group comprising from 20 to 40 carbon atoms), alone or as a mixture.
  • a wax is notably sold under the names Kester Wax K 82 P®, Hydroxypolyester K 82 P® and Kester Wax K 80 P® by the company Koster Keunen.
  • microwaxes in the compositions of the invention; mention may notably be made of carnauba microwaxes, such as the product sold under the name MicroCare 350® by the company Micro Powders, synthetic-wax microwaxes, such as the product sold under the name MicroEase 114S® by the company Micro Powders, microwaxes constituted of a mixture of carnauba wax and polyethylene wax, such as the products sold under the names Micro Care 300® and 310® by the company Micro Powders, microwaxes constituted of a mixture of carnauba wax and of synthetic wax, such as the product sold under the name Micro Care 325® by the company Micro Powders, polyethylene microwaxes, such as the products sold under the names Micropoly 200®, 220®, 220L® and 250S® by the company Micro Powders, and polytetrafluoroethylene microwaxes, such as the products sold under the names Microslip 519® and 519 L® by the company Micro Powders.
  • the waxes are preferably chosen from mineral waxes, for instance paraffin, petroleum jelly, lignite or ozokerite wax; plant waxes, for instance cocoa butter, shea butter or cork fibre or sugar cane waxes, olive tree wax, rice bran wax, hydrogenated jojoba wax, ouricury wax, carnauba wax, candelilla wax, esparto grass wax, or absolute waxes of flowers, such as the essential wax of blackcurrant blossom sold by the company Bertin (France); waxes of animal origin, for instance beeswaxes or modified beeswaxes (cera bellina), spermaceti, lanolin wax and lanolin derivatives; microcrystalline waxes; and mixtures thereof.
  • mineral waxes for instance paraffin, petroleum jelly, lignite or ozokerite wax
  • plant waxes for instance cocoa butter, shea butter or cork fibre or sugar cane waxes, olive tree wax, rice bran wax, hydrogenated jojoba wax
  • Ceramides, or ceramide analogues, such as glycoceramides, that may be used in the compositions according to the invention, are known; mention may in particular be made of ceramides of classes I, II, III and V according to the Dawning classification.
  • ceramides or analogues thereof that may be used preferably correspond to the following formula: in which: - R1 denotes a linear or branched, saturated or unsaturated alkyl group, derived from C14-C30 fatty acids, it being possible for this group to be substituted with a hydroxyl group in the alpha position, or a hydroxyl group in the omega position esterified with a saturated or unsaturated C16-C30 fatty acid;
  • R2 denotes a hydrogen atom or a (glycosyl)n group, a (galactosyl)m group or a sulfogalactosyl group, in which n is an integer ranging from 1 to 4 and m is an integer ranging from 1 to 8;
  • R3 denotes a C15-C26 hydrocarbon-based group which is saturated or unsaturated in the alpha position, it being possible for this group to be substituted with one or more C1 -C14 alkyl groups; it being understood that, in the case of natural ceramides or glycoceramides, R3 can also denote a C15-C26 a-hydroxyalkyl group, the hydroxyl group being optionally esterified with a C16-C30 a-hydroxy acid.
  • the ceramides that are more particularly preferred are the compounds for which R1 denotes a saturated or unsaturated alkyl derived from C16-C22 fatty acids; R2 denotes a hydrogen atom; and R3 denotes a saturated or unsaturated linear C15 group.
  • Ri denotes a saturated or unsaturated alkyl radical derived from C12-C22 fatty acids
  • R2 denotes a galactosyl or sulfogalactosyl radical
  • the liquid fatty substances have a melting point of less than or equal to 25°C, preferably of less than or equal to 20°C, at atmospheric pressure (1 .013 x 10 5 Pa).
  • the liquid fatty substances are not (poly)oxyalkylenated.
  • the fatty alcohols, esters and acids more particularly contain at least one saturated or unsaturated, linear or branched hydrocarbon-based group comprising from 6 to 40 and better still from 8 to 30 carbon atoms, which is optionally substituted, in particular with one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
  • the liquid hydrocarbons may be Ce to Cis liquid hydrocarbons and be linear, branched or optionally cyclic; they are preferably chosen from Cs-C , notably C10- C14, alkanes. Examples that may be mentioned include hexane, cyclohexane, undecane, dodecane, isododecane, tridecane or isoparaffins, such as isohexadecane or isodecane, and mixtures thereof.
  • the liquid hydrocarbons may also be chosen from those comprising more than 16 carbon atoms, which may be linear or branched, of mineral or synthetic origin; mention may be made of liquid paraffins or liquid petroleum jelly, polydecenes, hydrogenated polyisobutene, such as Parleam®, and mixtures thereof.
  • the triglyceride oils of plant or synthetic origin may be chosen from liquid fatty acid triglycerides including from 6 to 30 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, capryl ic/capric acid triglycerides, for instance those sold by the company Stearinerie Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, jojoba oil and shea butter oil, and mixtures thereof.
  • liquid fatty acid triglycerides including from 6 to 30 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil,
  • the liquid fatty alcohols may be chosen from linear or branched, saturated or unsaturated alcohols, preferably unsaturated or branched alcohols, including from 6 to 40 carbon atoms and preferably from 8 to 30 carbon atoms. Examples that may be mentioned include octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2- undecylpentadecanol, isostearyl alcohol, oleyl alcohol, linolenyl alcohol, ricinoleyl alcohol, undecylenyl alcohol and linoleyl alcohol, and mixtures thereof.
  • liquid esters of fatty acids and/or fatty alcohols other than the triglycerides mentioned above mention may notably be made of esters of saturated or unsaturated, linear Ci to C26 or branched C3 to C26, aliphatic mono- or polyacids and of saturated or unsaturated, linear Ci to C26 or branched C3 to C26, aliphatic mono- or polyalcohols, the total carbon number of the esters being greater than or equal to 6, more advantageously greater than or equal to 10.
  • At least one from among the alcohol and the acid from which the esters of the invention are derived is branched.
  • dihydroabietyl behenate octyldodecyl behenate; isocetyl behenate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; isostearyl octanoate; isocetyl octanoate; octyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methyl acetyl ricinoleate; octyl isononanoate; 2-ethylhexyl isononate; octyldodecyl
  • ethyl palmitate or isopropyl palmitate alkyl myristates, such as isopropyl or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isodecyl neopentanoate, isostearyl neopentanoate and mixtures thereof.
  • esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1 -C22 alcohols and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of C2-C26 dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used.
  • composition may also comprise, as fatty ester, sugar esters and diesters of C6 to C30 and preferably C12 to C22 fatty acids.
  • sugar esters refers to oxygen-bearing hydrocarbon-based compounds bearing several alcohol functions, with or without aldehyde or ketone functions, and which include at least 4 carbon atoms.
  • sugars may be monosaccharides, oligosaccharides or polysaccharides.
  • suitable sugars include sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, notably alkyl derivatives, such as methyl derivatives, for instance methylglucose.
  • the sugar esters of fatty acids may be chosen notably from the group comprising the esters or mixtures of esters of sugars described above and of linear or branched, saturated or unsaturated C6 to C30 and preferably C12 to C22 fatty acids. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
  • esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters, and mixtures thereof.
  • These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates, arachidonates or mixtures thereof notably such as the mixed oleo-palmitate, oleo-stearate and palmito-stearate esters.
  • monoesters and diesters and notably sucrose, glucose or methylglucose mono- or di-oleates, -stearates, -behenates, -oleopalmitates, -linoleates, -linolenates and -oleostearates, and mixtures thereof.
  • liquid ester of a monoacid and of a monoalcohol Preferably, use will be made of a liquid ester of a monoacid and of a monoalcohol.
  • the fatty substances are chosen from triglyceride oils of plant or synthetic origin, liquid esters of a fatty acid and/or a fatty alcohol other than triglycerides, liquid Ce-Ci8 hydrocarbons, solid fatty alcohols, solid esters of fatty acids and/or of fatty alcohols, and mixtures thereof.
  • the composition according to the invention may comprise the fatty substance(s) in a total amount ranging from 0.1 % to 20% by weight, better still from 1 % to 18% by weight, preferentially from 2% to 15% by weight, even better still from 5% to 12% by weight, relative to the total weight of the composition.
  • composition used according to the invention advantageously comprises water, notably in a concentration preferably ranging from 50% to 95% by weight, for example from 55% to 90% by weight, notably from 60% to 85% by weight, better still from 65% to 85% by weight, relative to the total weight of the composition.
  • the pH of the composition may be between 2.5 and 8, preferentially between 3 and 7, or even between 4 and 6.
  • composition used according to the invention may optionally comprise one or more preferably hydrophilic (water-soluble or water-miscible) organic solvents which are liquid at 25°C, 1 atm, which may be chosen from Ci-Ce aliphatic or aromatic monoalcohols, C2-C8 polyols and C3-C7 polyol ethers.
  • organic solvent is chosen from C2-C4 mono-, di- or tri-diols. It may advantageously be chosen from ethanol, isopropanol, benzyl alcohol, glycerol, 1 ,2-propanediol (propylene glycol) and mixtures thereof.
  • composition used according to the invention may also comprise at least one or more standard cosmetic ingredients notably chosen from thickeners, gelling agents, which are both different from the polymers described above; sunscreens; antidandruff agents; antioxidants; chelating agents; reducing agents; oxidation bases, couplers, oxidizing agents, direct dyes; hair-straightening agents; nacreous agents and opacifiers; micas, nacres, glitter flakes; plasticizers or coalescers; pigments; fillers; fragrances; basifying or acidifying agents; silanes.
  • sunscreens notably chosen from thickeners, gelling agents, which are both different from the polymers described above
  • sunscreens antidandruff agents
  • antioxidants antioxidants
  • chelating agents reducing agents; oxidation bases, couplers, oxidizing agents, direct dyes; hair-straightening agents; nacreous agents and opacifiers; micas, nacres, glitter flakes; plasticizers or coalescers; pigments; fill
  • the hair composition used in the process according to the invention may comprise:
  • R represents a hydrogen atom or a saturated, linear or branched, (Ci-C4)alkyl group, optionally interrupted with a -S- heteroatom and/or optionally substituted with one or two groups chosen from hydroxyl, amino or -NH- C(NH)-NH2; better still, R represents a hydrogen atom; preferably present in a total content from 0.6% to 10% by weight, notably from 0.7% to 8% by weight, better still from 0.8% to 7% by weight, relative to the total weight of the composition;
  • hydroxylated polycarboxylic acids comprising from 4 to 6 carbon atoms, from 1 to 3 OH groups and 2 or 3 COOH groups, and/or salts thereof, preferably present in a total content from 0.5% to 10% by weight, notably from 1 % to 8% by weight, better still from 1 .5% to 6% by weight;
  • associative polymers which are preferably nonionic, better still chosen from polyether polyurethanes; preferably present in the composition in a total content ranging from 0.01 % to 10% by weight, preferentially from 0.05% to 5% by weight, more preferentially from 0.1 % to 1 .5% by weight, relative to the total weight of the composition;
  • silicones preferably chosen from amino silicones; preferably present in a total content ranging from 0.3% to 5% by weight, better still from 0.4% to 4% by weight, preferentially from 0.6% to 3% by weight and more preferentially from 0.7% to 2.5% by weight, relative to the total weight of the composition;
  • cationic surfactants preferably chosen from those of formula (II) above, those of formula (V) above, those of formula (VI) above, and their mixtures, better still from those of formulae (II) and/or of formula (VI) above; preferably present in a total amount ranging from 0.1 % to 10% by weight, better still from 0.2% to 8% by weight, preferentially from 0.3% to 7% by weight, even better still from 0.5% to 5% by weight, relative to the total weight of the composition;
  • cationic polysaccharides notably chosen from cationic celluloses and/or galactomannan gums; preferably present in a total amount ranging from 0.01 % to 10% by weight, better still from 0.05% to 5% by weight, even better still from 0.1 % to 2% by weight, relative to the total weight of the composition;
  • nonionic polysaccharides notably chosen, alone or as a mixture, from nonionic guar gums optionally modified with (poly)hydroxy(Ci-Ce)alkyl groups; preferably present in a total amount ranging from 0.01 % to 10% by weight, better still from 0.05% to 5% by weight, even better still from 0.1 % to 2% by weight, relative to the total weight of the composition;
  • nonionic surfactants preferably present in a total content ranging from 0.05% to 10% by weight, preferably from 0.1 % to 5% by weight, preferentially from 0.2% to 3% by weight, relative to the total weight of the composition according to the invention.
  • composition A according to the invention and the following comparative composition A’ were prepared from the ingredients shown in the tables below (g% AM):
  • Composition A is in the form of a cream and may advantageously be used in rinse- out mode after or before shampooing. This composition may be used for disentangling of the hair, with the addition of care, sheen and strength (slightly less suppleness than classic care treatments, body and a mass effect).
  • the hair is soft, hydrated and more shiny; it is considered stronger and less prone to breakage.
  • the composition thus has strengthening properties and makes it possible to reduce the amount of calcium contained in the hair fibre application after application.
  • the strengthening is measured using the DSC technique.
  • the measurements are performed on locks that have previously been bleached manually and then treated five times (or ten times) according to the following protocol: the lock is washed with a neutral shampoo, then rinsed, 2 g of the composition to be tested are applied to each 5.7 g lock of hair, the treatment is left on for 5 minutes, then rinsed again.
  • the differential scanning calorimetry (DSC) technique is known to those skilled in the art as a method for quantifying the strengthening of proteins in the cortex of keratin fibres (Kinetics of the changes imparted to the main structural components of human hair by thermal treatment, F.-J. Wortmann and H. Deutz, J. Appl. Polym Sci. , 48, 137 (1993).
  • the principle of the test is to measure the protein denaturing temperature. It is widely acknowledged that the higher the protein denaturing temperature, the better the integrity of the proteins of the cortex, which reflects the reduction in fibre breakage.
  • the denaturing temperature is directly linked to the bonding density of the keratin proteins present in the cortex.
  • the lower the denaturing temperature the lower the bonding density between the proteins: the disulfide bridges break and the cortex is damaged.
  • a difference of 2°C is acknowledged by those skilled in the art as a significant modification.
  • the machine used for taking the measurements is a TA Instruments DSC Q20 reference instrument. This machine measures the energy flow during heating of the sample. The temperature of maximum energy flow represents the denaturing temperature.
  • composition according to the invention increases the bonding density of the keratin proteins presents in the cortex of the treated hair, thus enabling repair of the damaged hair.
  • the denaturing temperature for the locks treated according to the present invention is better than that measured for natural, undamaged hair, thus demonstrating that the hair has been repaired.
  • composition according to the invention was prepared from the ingredients shown in the tables below (g% AM):
  • composition is in the form of a lotion and may advantageously be used, without rinsing, before shampooing or after shampooing and before using a mask or a hair conditioner without rinsing.
  • This composition can be used for disentangling the hair, with the addition of care, sheen and strength (body and mass effect).
  • the hair is soft, hydrated and more shiny; it is considered stronger and less prone to breakage.
  • the composition thus has strengthening properties and makes it possible to reduce the amount of calcium contained in the hair fibre application after application.
  • the strengthening is measured by DSC, according to the method described above.
  • the measurements are performed on locks previously bleached manually and then treated five (or ten) times according to the following protocol: the lock is washed with a conventional neutral shampoo, then rinsed, 2 g of the composition according to the invention are applied per 5.7 g lock of hair, and then, without rinsing, 2 g of a conventional hair mask are applied, the mask is left on for 5 minutes and then rinsed once again.
  • This routine according to the invention is compared with the following comparative routine (without application of the composition of the invention): the lock is washed with a conventional neutral shampoo, then rinsed, 2 g of a conventional hair mask (the same as in the routine according to the invention) are applied, the mask is left on for 5 minutes and then rinsed again.
  • composition according to the invention increases the bonding density of the keratin proteins presents in the cortex of the treated hair, thus enabling repair of the damaged hair.

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Abstract

The present invention relates to a cosmetic hair treatment process, comprising at least two successive steps of applying a cosmetic composition comprising: - one or more compounds of amino acid type present in a total content of at least 0.6% by weight, relative to the total weight of the composition, and - one or more hydroxylated polycarboxylic acids comprising 2 to 8 carbon atoms, and/or salts thereof, present in a total content of at least 0.5% by weight, relative to the total weight of the composition.

Description

DESCRIPTION
TITLE: Cosmetic hair treatment process, comprising a multi-application of a composition comprising amino acids and specific hydroxy carboxylic acids
The present invention relates to a cosmetic hair treatment process, comprising at least two successive steps of applying a composition comprising one or more compounds of amino acid type and one or more specific hydroxy carboxylic acids.
Consumers worldwide are generally in contact with highly varied sources of water which are not without impact on the hair, notably with regard to their cosmetic properties, and/or the performance qualities of hair products.
“Mineral” waters contain, for example, variable amounts of minerals present in the form of dissolved ions, such as calcite (present in the form of calcium), dolomite (present in the form of calcium and magnesium), magnetite (present in the form of iron) and chalcanthite (present in the form of copper). “Hard” waters are also concentrated in minerals, such as calcium and magnesium, and swimming pool waters are for their part concentrated in copper salts originating from algicides used in the treatment of swimming pools.
Hair has a strong tendency to absorb these minerals and/or their metal salts because of the presence, at the surface thereof, of anionic functional groups which correspond in particular to the sulfonic or carboxylic functional groups of keratin. Furthermore, the isoelectric point of the individual hair is generally described between 3.2 and 4. The result of this is that, in everyday life, the pH of the water applied to the hair is greater than such values, which results in a negatively charged fibre.
Minerals, very often polyvalent cations, will thus be attracted and captured by this negatively charged fibre with the formation of chemical bonds, which prevent them from being released by conventional hair treatment processes. This results in a possible accumulation of minerals on the hair with the passage of time. Such an attaching depends not only on the hardness of the water, on the frequency and/or duration of exposure of the hair to the water in question but also on the nature and the length of the hair (in particular porosity and charge) and also on its state of damage.
The accumulation of these minerals and/or of their metal salts can result in modifications to the hair fibre and in particular in a more or less marked modification of the cosmetic properties of the individual hair. Thus, an accumulation of calcium and of magnesium can result in dry hair lacking in gloss, whereas an accumulation of copper can result in the hair turning green.
In addition, the accumulation of the metal (iron, copper, for example) salts can accelerate the damage caused to the hair because they catalyse oxidation/reduction reactions and generate hydroxyl radicals HO° which can be harmful to the keratin fibre, including at low contents.
This can result in a photodegradation of the fibre, in a lightening of the fibre, and also in a detrimental change in the properties of the hair, which can result in premature breakage of the individual hair; these phenomena are very particularly observed during the subsequent use of lightening products or dyeing products.
In other words, the hair can become less resistant, more weakened, indeed even break more easily, or also lose its sheen, due to the accumulation of minerals and/or their metal salts.
There thus exists a real need to have available a means which makes it possible to combat the accumulation of the metal ions, resulting from minerals and metal salts dissolved in water, indeed even to make it possible to extract them from keratins fibres, in order to limit their negative impacts and to overcome all of the abovementioned disadvantages.
The use of the composition described hereinbelow, in a repeated manner, makes it possible to achieve this aim.
One subject of the present invention is thus a cosmetic hair treatment process, comprising at least two successive steps of applying a cosmetic composition comprising:
- one or more compounds of amino acid type present in a total content of at least 0.6% by weight, relative to the total weight of the composition, and
- one or more hydroxylated polycarboxylic acids comprising from 2 to 8 carbon atoms, and/or salts thereof, present in a total content of at least 0.5% by weight, relative to the total weight of the composition.
It has been found that the process according to the invention makes it possible to improve the resistance to breakage of the hair, to strengthen the hair and also to significantly limit its reduction or loss of sheen, undesirable effects liable to be caused by the presence of metal ions, notably copper or calcium ions, within said fibres.
After performing the process, the fibres appear to be strengthened, said strengthening being improved with successive applications of the composition.
It has also been found that the composition used in the context of the invention makes it possible to contribute conditioning properties to the hair, notably a smooth feel, softness, sheen and facilitated disentangling, and to do so while contributing strength, body and a bulk effect to the head of hair.
The process according to the invention is particularly suitable for hair that has been sensitized, weakened and/or damaged, notably as a result of physical (repeated brushing) and/or chemical treatments, for example dyeing, bleaching, perming and/or straightening.
It is also particularly suitable for the cosmetic treatment of hair laden with metals, notably laden with metals in contents of at least 100 ppm, better still in contents of at least 200 ppm; in particular laden with copper, notably in contents of at least 100 ppm, better still in contents of at least 200 ppm and/or laden with calcium notably in contents of at least 4000 ppm, better still in contents of at least 10 000 ppm.
The hair treatment process according to the invention comprises at least two successive steps consisting in applying the composition as defined above to the hair.
In other words, the composition is applied to the hair several times successively, that is to say that the steps of applying the composition according to the invention are performed one after the other with or without an intermediate rinsing step.
Preferentially, the process according to the invention involves a step of rinsing the hair at least between two successive steps of applying the composition.
The leave-on time of the composition according to the invention on the hair can vary between several seconds (10 seconds for example) and several minutes (5 to 60 minutes for example), preferably between 1 and 30 minutes, better still between 2 and 15 minutes.
The application to the hair may be performed for example by means of a comb, a fine brush, with the aid of a coarse brush or with the fingers.
Between each successive step of applying the composition, the hair may be rinsed and/or may be dried.
The rinsing may be performed with water or a shampoo, after a possible leave-on time. The hair can then be squeezed dry, optionally washed using a standard shampoo and then dried.
The rinsing step may also be followed by a drying step, for example at room temperature (25°C) or at a temperature greater than 40°C. Preferably, the hair is dried, in addition to a supply of heat, with a flow of air. During drying, a mechanical action may be exerted on the locks, such as combing, brushing, or running the fingers through. The drying step of the process of the invention may be performed with a hood, a hairdryer or a straightening iron. When the drying step is performed with a hood or a hairdryer, the drying temperature is between 40°C and 110°C, preferably between 50°C and 90°C. When the drying step is performed with a straightening iron, the drying temperature is between 110°C and 220°C, preferably between 130°C and 200°C.
The hair treatment process according to the invention may comprise more than two successive steps of applying the composition as defined above to the hair, for example at least 3 successive steps, or even at least 4 successive steps. These successive applications may also be performed over several weeks, or even several months.
The time between each application step may advantageously be between 1 day and several days, for example 1 day to 7 days, which corresponds to a weekly application of the composition, or between 2 and 4 days, which corresponds to a twice-weekly application of the composition.
In the text hereinbelow, unless otherwise indicated, the limits of a range of values are included in that range, notably in the expressions “between” and “ranging from ... to ...”.
Moreover, the expression “at least one” used in the present description is equivalent to the expression “one or more”, and may be replaced therewith.
Compounds of amino acid type
The composition used in the context of the present invention comprises one or more compounds of amino acid type.
For the purposes of the present invention, the term “compound of amino acid type” means an organic compound comprising one or more carboxylic acid and/or sulfonic acid functions and one or more amine functions, it being possible for the amine function(s) to be endocyclic, optionally in salt form.
Preferably, the compound(s) of amino acid type are chosen from compounds of amino acid type comprising only one or more carboxylic acid functions (thus not comprising any sulfonic acid functions) and/or salts thereof. Said compounds are also called compounds of aminocarboxylic acid type and are particularly preferred.
Preferably, the composition according to the present invention comprises one or more compounds of amino acid type chosen from the compounds corresponding to formula (I) below and/or salts thereof.
The compounds of amino acid type may thus correspond to formula (I):
Figure imgf000005_0001
in which p is an integer equal to 1 or 2, it being understood that:
- when p = 1 , R forms, with the nitrogen atom, a saturated heterocycle comprising from 5 to 8 ring members, preferably 5 ring members, it being possible for this ring to be substituted with one or more groups chosen from hydroxyl or (Ci-C4)alkyl;
- when p = 2, R represents a hydrogen atom or a saturated, linear or branched, (Ci- Ci2)alkyl, preferably (Ci-C4)alkyl, group, optionally interrupted with one or more heteroatoms or groups chosen from -S-, -NH- or -C(NH)- and/or optionally substituted with one or more groups chosen from hydroxyl (-OH), amino (-NH2), - SH, -COOH, -CONH2 or -NH-C(NH)-NH2.
Preferably, when p = 1 , R forms, with the nitrogen atom, a saturated heterocycle comprising 5 ring members, this ring not being substituted.
Preferably, p = 2.
Preferably, when p = 2, R represents a hydrogen atom or a saturated, linear or branched, (Ci-C4)alkyl group, optionally interrupted with a -S- heteroatom and/or optionally substituted with one or two groups chosen from hydroxyl, amino or -NH- C(NH)-NH2.
Preferentially, p = 2 and R represents a hydrogen atom.
The compounds of amino acid type may also be a salt of a compound of formula (I). These salts comprise the salts with organic or mineral bases, for example the salts of alkali metals, for instance the lithium, sodium or potassium salts; the salts of alkaline-earth metals, for instance the magnesium or calcium salts, and the zinc salts.
The compounds of amino acid type may be in the form of an optical isomer of L, D or DL configuration, preferably of L configuration.
As examples according to the present invention of compounds in the form of an optical isomer of L configuration, mention may be made of L-proline, L-methionine, L-serine, L-arginine and L-lysine.
Preferably, the compound(s) of amino acid type according to the invention are chosen from glycine, proline, methionine, serine, arginine, lysine, their salts (notably alkali metal, alkaline-earth metal or zinc salts) and mixtures thereof.
Preferably, the compound(s) of amino acid type according to the invention are chosen from glycine, proline, methionine, serine, arginine, salts thereof and mixtures thereof.
Better still, the compound of amino acid type is chosen from glycine, salts thereof (notably alkali metal, alkaline-earth metal or zinc salts) and mixtures thereof.
As glycine salts according to the present invention, mention may be made of sodium glycinate, zinc glycinate, calcium glycinate, magnesium glycinate, manganese glycinate and potassium glycinate, preferably sodium glycinate and potassium glycinate.
Preferably, the compound of amino acid type is glycine.
The total content of compound(s) of amino acid type present in the composition according to the invention is at least 0.6% by weight, relative to the total weight of the composition. This content may range from 0.6% to 10% by weight, notably from 0.7% to 8% by weight, better still from 0.8% to 7% by weight, relative to the total weight of the composition. In particular, the total content of compound(s) of aminocarboxylic acid type in the composition according to the invention may range from 0.6% to 10% by weight, notably from 0.7% to 8% by weight, better still from 0.8% to 7% by weight, relative to the total weight of the composition.
Better still, the total content of compound(s) of amino acid type chosen from glycine, proline, methionine, serine, arginine, lysine, salts thereof and mixtures thereof in the composition according to the invention may range from 0.6% to 10% by weight, notably from 0.7% to 8% by weight, better still from 0.8% to 7% by weight, relative to the total weight of the composition.
Most particularly, the total content of compound(s) of amino acid type chosen from glycine, salts thereof and mixtures thereof in the composition according to the invention may range from 0.6% to 10% by weight, notably from 0.7% to 8% by weight, better still from 0.8% to 7% by weight, relative to the total weight of the composition.
Better still, the glycine content in the composition according to the invention may range from 0.6% to 10% by weight, notably from 0.7% to 8% by weight, better still from 0.8% to 7% by weight, relative to the total weight of the composition.
Hydroxy polycarboxylic acids
The composition used according to the invention also comprises one or more hydroxylated polycarboxylic acids comprising from 2 to 8 carbon atoms, and/or salts thereof.
These polyacids are different from the compounds of amino acid type described above.
Said polyacids comprise at least two COOH groups (in acid or salified form); they may comprise two to three COOH groups (in acid or salified form).
They also comprise at least one OH group but may comprise several thereof, notably from two to three OH groups.
Preferably, they comprise in total from four to six carbon atoms and their hydrocarbon-based chain is saturated and linear.
Advantageously, the hydroxylated polycarboxylic acids and/or salts thereof comprise in total from four to six carbon atoms, from one to three OH groups and from two to three COOH groups (in acid or salified form).
The salts of these polyacids comprise the salts with organic or mineral bases, for example the salts of alkali metals, such as the lithium, sodium or potassium salts; the salts of alkaline-earth metals, such as the magnesium or calcium salts, and the zinc salts. The alkali metal or alkaline-earth metal salts are preferred and in particular the sodium salts. Preferably, the hydroxylated polycarboxylic acids or salts thereof are chosen from a-hydroxy acids and salts thereof, and notably from tartaric acid or citric acid, and salts thereof, notably alkali metal or alkaline-earth metal salts; most particularly sodium citrate and/or sodium tartrate; better still citric acid or salts thereof, notably alkali metal or alkaline-earth metal salts, such as sodium citrate.
The total content of hydroxylated polycarboxylic acids comprising in total from two to eight carbon atoms, and/or salts thereof, present in the composition according to the invention is at least 0.5% by weight, relative to the total weight of the composition. This content may range from 0.5% to 10% by weight, notably from 1 % to 8% by weight, better still from 1.5% to 6% by weight, relative to the total weight of the composition.
In particular, the total content of hydroxylated polycarboxylic acids comprising in total from four to six carbon atoms, from one to three OH groups and two or three COOH groups, or salts thereof, present in the composition according to the invention may range from 0.5% to 10% by weight, notably from 1 % to 8% by weight, better still from 1 .5% to 6% by weight, relative to the total weight of the composition.
Most particularly, the total content of hydroxylated polycarboxylic acids chosen from tartaric acid and/or citric acid, and salts thereof, notably alkali metal or alkaline-earth metal salts, in the composition according to the invention may range from 0.5% to 10% by weight, notably from 1 % to 8% by weight, better still from 1.5% to 6% by weight, relative to the total weight of the composition.
Better still, the content of citric acid and/or salts thereof in the composition according to the invention may range from 0.5% to 10% by weight, notably from 1 % to 8% by weight, better still from 1.5% at 6% by weight, relative to the total weight of the composition.
Associative polymer
The composition used according to the invention may optionally comprise one or more associative polymers. Preferably, the associative polymers are nonionic.
For the purposes of the present invention, the term “polymer” means any compound derived from the polymerization by polycondensation or from the radical polymerization of monomers, at least one of which is other than an alkylene oxide, and of a monofunctional compound of formula RX, R denoting an optionally hydroxylated C10-C30 alkyl or alkenyl group, and X denoting a carboxylic acid, amine, amide, hydroxyl or ester group. All the compounds resulting solely from the simple condensation of an alkylene oxide with a fatty alcohol, a fatty ester, a fatty acid, a fatty amide or a fatty amine are in particular excluded.
For the purposes of the present invention, the term “associative polymer” means an amphiphilic polymer that is capable, in an aqueous medium, of reversibly combining with itself or with other molecules. It generally includes, in its chemical structure, at least one hydrophilic region or group and at least one hydrophobic region or group. The associative polymers according to the invention are polymers comprising at least one fatty chain including from 8 to 30 carbon atoms, the molecules of which are capable, in the formulation medium, of combining with each other or with molecules of other compounds. Preferably, the fatty chain includes from 10 to 30 carbon atoms.
A particular case of associative polymers is amphiphilic polymers, that is to say polymers including one or more hydrophilic parts or groups which make them water- soluble and one or more hydrophobic regions or groups (including at least one fatty chain) via which the polymers interact and assemble with each other or with other molecules.
The term “hydrophobic group” means a group or a polymer containing a saturated or unsaturated, linear or branched hydrocarbon-based chain, which may contain one or more heteroatoms such as P, O, N or S, or a radical containing a perfluoro or silicone chain. When it denotes a hydrocarbon-based group, the hydrophobic group includes at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and preferentially from 18 to 30 carbon atoms. Preferentially, the hydrocarbon-based hydrophobic group originates from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol, such as stearyl alcohol, dodecyl alcohol or decyl alcohol, or else from a polyalkylenated fatty alcohol, such as Steareth-100. It may also denote a hydrocarbon-based polymer, for instance polybutadiene.
For the purposes of the present invention, the term “fatty chain” means a linear or branched alkyl or alkenyl chain including at least 8 carbon atoms, preferably from 8 to 30 carbon atoms and better still from 10 to 22 carbon atoms.
For the purposes of the present invention, the term “fatty compound”, for instance a fatty alcohol, a fatty acid or a fatty amide, means a compound comprising, in its main chain, at least one saturated or unsaturated hydrocarbon-based chain, such as an alkyl or alkenyl chain, including at least 8 carbon atoms, preferably from 8 to 30 carbon atoms and better still from 10 to 22 carbon atoms.
Among the the anionic associative polymers, mention may notably be made of:
- (A) those including at least one hydrophilic unit and at least one fatty-chain allyl ether unit; and more particularly those: of which the hydrophilic unit is constituted by an ethylenic unsaturated anionic monomer, even more particularly by a vinylcarboxylic acid and most particularly by an acrylic acid or a methacrylic acid or mixtures thereof; and of which the fatty-chain allyl ether unit corresponds to the monomer of formula (I’) below: CH2=C(R’)-CH2OBnR in which R’ denotes H or CH3, B denotes an ethyleneoxy radical, n ranges from 0 to 100 and R denotes a hydrocarbon-based radical chosen from the alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl radicals, comprising from 8 to 30 carbon atoms, preferably from 10 to 24 carbon atoms and even more particularly from 12 to 18 carbon atoms. Preferably, R’ denotes H, n = 10 and R denotes a stearyl (Cis) radical. Among these anionic associative polymers, preference is particularly given to polymers formed from 20% to 60% by weight of acrylic acid and/or of methacrylic acid, from 5% to 60% by weight of C1-C4 alkyl (meth)acrylates, from 2% to 50% by weight of fatty-chain allyl ether of formula (I’) and from 0% to 1 % by weight of a crosslinking agent which is preferably a copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylenebisacrylamide.
Preference is most particularly given to crosslinked terpolymers of methacrylic acid, of ethyl acrylate and of polyethylene glycol (10 EO) stearyl alcohol ether (Steareth- 10), notably the product sold by the company BASF under the name Salcare SC80, which is a 30% aqueous emulsion of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate and of Steareth-10 allyl ether (40/50/10) having the INCI name Steareth-10 Allyl Ether/Acrylates Copolymer;
- (B) those including at least one hydrophilic unit of unsaturated olefinic carboxylic acid type and at least one hydrophobic unit of (C -C3o)alkyl ester of unsaturated carboxylic acid type.
These polymers are preferably chosen from those for which the hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the monomer of formula (II) below:
Figure imgf000010_0001
in which R1 denotes H or CH3 or C2H5, and for which the hydrophobic unit of (C10- C3o)alkyl ester of unsaturated carboxylic acid type corresponds to the monomer of formula (III) below:
Figure imgf000010_0002
in which R2 denotes H, CH3 or C2H5 and R3 denotes a C10-C30 and preferably C12- C22 alkyl radical.
(C10-C30) Alkyl esters of unsaturated carboxylic acids in accordance with the invention comprise, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.
Among these anionic associative polymers, use will more particularly be made of polymers formed from a mixture of monomers comprising: (i) (meth)acrylic acid, (ii) an ester of formula (III) described above and in which R2 denotes H or CH3 and R3 denotes an alkyl radical containing from 12 to 22 carbon atoms, and optionally (iii) a crosslinking agent which is a well-known copolymerizable polyethylenic unsaturated monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate and methylenebisacrylamide. Among anionic associative polymers of this type, preference is more particularly given, to those constituted of from 95% to 60% by weight of (meth)acrylic acid, 4% to 40% by weight of C10-C30 alkyl acrylate and 0% to 6% by weight of crosslinking polymerizable monomer, or else to those constituted of from 98% to 96% by weight of (meth)acrylic acid, 1 % to 4% by weight of C10-C30 alkyl acrylate and 0.1 % to 0.6% by weight of crosslinking polymerizable monomer, such as those described previously.
Mention may in particular be made of the products sold by the company Lubrizol under the trade names Pemulen TR1 , Pemulen TR2, Carbopol 1382, Carbopol ETD 2020, Carbopol Ultrez 20, Carbopol Ultrez 21 , having the INCI name Acrylates/C I Q- 30 Alkyl Acrylate Crosspolymer, and even more preferably Pemulen TR1 and Carbopol 1382;
- (C) maleic anhydride/Cso-Css a-olefin/alkyl maleate terpolymers, such as the maleic anhydride/Cso-Css a-olefin/isopropyl maleate copolymer, in particular the product sold under the name Performa V 1608 by the company Newphase Technologies (INCI name: C30-38 Olefin/lsopropyl Maleate/MA Copolymer);
- (D) acrylic terpolymers comprising (a) from 20% to 70% by weight of an a,(3- monoethylenically unsaturated carboxylic acid, (b) from 20% to 80% by weight of a non-surface-active a,[3-monoethylenically unsaturated monomer other than (a), and (c) from 0.5% to 60% by weight of a nonionic monourethane which is the reaction product of a monohydric surfactant with a monoethylenically unsaturated monoisocyanate.
Mention may notably be made of the methacrylic acid/methyl acrylate/dimethyl(meta-isopropenyl)benzyl isocyanate of ethoxylated (40 EO) behenyl alcohol terpolymer, notably as a 25% aqueous dispersion, such as the product Viscophobe DB1000 sold by the company Amerchol (Dow Chemical), having the INC name Polyacrylate-3;
- (E) copolymers including among their monomers (i) an a,p-monoethylenically unsaturated carboxylic acid, such as acrylic or methacrylic acid, and (ii) an ester of an a,p-monoethylenically unsaturated carboxylic acid, notably acrylic or methacrylic acid, and of fatty alcohol, notably C8-C32 fatty alcohol, which is oxyalkylenated, notably comprising from 2 to 100 mol of ethylene oxide, in particular from 4 to 50, or even from 10 to 40 EO.
Mention may in particular made, as monomers, of behenyl or stearyl (meth)acrylate comprising 10 to 40 EO, in particular 18 to 30 EO.
Preferentially, these compounds also comprise, as monomer, an ester of an a,(3- monoethylenically unsaturated carboxylic acid and of a C1-C4 alcohol, notably a C1- C4 alkyl (meth)acrylate.
Preferably, these copolymers comprise at least one (meth)acrylic acid monomer, at least one C1-C4 alkyl (meth)acrylate monomer and at least one C8-C32 alkyl (meth)acrylate monomer which is oxyethylenated, comprising from 2 to 100 mol EO, in particular from 4 to 50 EO, or even from 10 to 40 EO.
By way of example, mention may be made of Aculyn 22 sold by the company Rohm and Haas, which is an oxyalkylenated methacrylic acid/ethyl acrylate/stearyl methacrylate terpolymer (INCI name: Acrylates/Steareth-20 Methacrylate Copolymer), or also of Aculyn 28 sold by Rohm and Haas, which is an oxyalkylenated methacrylic acid/ethyl acrylate/behenyl methacrylate terpolymer (INCI name: Acrylates/Beheneth-25 Methacrylate Copolymer), and also of the Novethix L-10 Polymer sold by Lubrizol;
- (F) associative polymers including at least one ethylenically unsaturated monomer bearing a sulfonic group, in free or partially or totally neutralized form and comprising at least one hydrophobic part.
Among the polymers of this type, mention may be made more especially of:
- crosslinked or non-crosslinked, neutralized or non-neutralized copolymers including from 15% to 60% by weight of AMPS (2-acrylamido-2- methylpropanesulfonic acid or salt) units and from 40% to 85% by weight of (Cs- Cie)alkyl (meth)acrylate units relative to the polymer, such as those described in patent application EP-A-750 899;
- terpolymers including from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of AMPS units and from 5 mol% to 80 mol% of n-(C6-C8)alkylacrylamide units, such as those described in patent US 5 089 578;
- copolymers of totally neutralized AMPS and of dodecyl methacrylate, and also copolymers of AMPS and of n-dodecylmethacrylamide, which are non-crosslinked and crosslinked;
- copolymers constituted of AMPS units and of steareth-25 methacrylate units, such as Aristoflex HMS® sold by the company Clariant (INCI name: Ammonium Acryloyldimethyltaurate/Steareth-25 Methacrylate Crosspolymer), or beheneth-25 methacrylate units, such as Aristoflex HMB (INCI name: Ammonium Acryloyldimethyltaurate/Beheneth-25 Methacrylate Crosspolymer) sold by the company Clariant, or also steareth-8 methacrylate units, such as Aristoflex SNC® from Clariant (INCI name: Ammonium Acryloyldimethyltaurate/Steareth-8 Methacrylate Copolymer);
- (G) associative polymers including at least one vinyllactam monomer and at least one a,p-monoethylenically unsaturated carboxylic acid monomer, such as terpolymers of vinylpyrrolidone, of acrylic acid and of C1-C20 alkyl methacrylate, for example lauryl methacrylate, such as the product sold by the company ISP under the name Acrylidone® LM (INCI name: VP/Acrylates/Lauryl Methacrylate Copolymer).
Among the cationic associative polymers, mention may be made of:
- (A) cationic associative polyurethanes, which may be represented by the general formula (la) below: R-X-(P)n-[L-(Y)m]r-L’-(P’)p-X’-R’ in which:
R and R’, which may be identical or different, represent a hydrophobic group or a hydrogen atom;
X and X’, which may be identical or different, represent a group including an amine function optionally bearing a hydrophobic group, or alternatively a group L”;
L, L’ and L”, which may be identical or different, represent a group derived from a diisocyanate;
P and P’, which may be identical or different, represent a group including an amine function optionally bearing a hydrophobic group;
Y represents a hydrophilic group; r is an integer between 1 and 100 inclusive, preferably between 1 and 50 inclusive and in particular between 1 and 25 inclusive; n, m and p are each, independently of each other, between 0 and 1000 inclusive; the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group.
Preferably, the only hydrophobic groups are the groups R and R' at the chain ends. One preferred family of cationic associative polyurethanes is the one corresponding to formula (la) described above, in which:
R and R’ both independently represent a hydrophobic group,
X and X’ each represent a group L”, n and p are integers that are between 1 and 1000 inclusive, and
L, L’, L”, P, P’, Y and m have the meanings given above.
Another preferred family of cationic associative polyurethanes is the one corresponding to formula (la) above in which: n = p = 0 (the polymers do not include any units derived from a monomer containing an amine function, incorporated into the polymer during the polycondensation), the protonated amine functions result from the hydrolysis of excess isocyanate functions, at the chain end, followed by alkylation of the primary amine functions formed with alkylating agents containing a hydrophobic group, i.e. compounds of the type RQ or R'Q, in which R and R' are as defined above and Q denotes a leaving group such as a halide or a sulfate, etc.
Yet another preferred family of cationic associative polyurethanes is the one corresponding to formula (la) above in which:
R and R’ both independently represent a hydrophobic group,
X and X’ both independently represent a group including a quaternary amine, n = p = 0, and
L, L’, Y and m have the meaning indicated above.
The number-average molecular mass (Mn) of the cationic associative polyurethanes is preferably between 400 and 500 000 inclusive, in particular between 1000 and 400 000 inclusive and ideally between 1000 and 300 000 inclusive.
Preferentially, the hydrocarbon-based group originates from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, for instance polybutadiene.
When X and/or X’ denote(s) a group including a tertiary or quaternary amine, X and/or X’ may represent one of the following formulae:
Figure imgf000014_0001
in which:
R2 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally including a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, 0 and P;
R1 and R3, which may be identical or different, denote a linear or branched C1-C30 alkyl or alkenyl radical or an aryl radical, at least one of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, 0 and P;
A- is a physiologically acceptable anionic counterion, such as a halide, for instance a chloride or bromide, or a mesylate.
The groups L, L’ and L” represent a group of formula:
Figure imgf000014_0002
in which:
Z represents -O-, -S- or -NH-; and
R4 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally including a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, 0 and P.
The groups P and P’ comprising an amine function may represent at least one of the following formulae:
Figure imgf000015_0001
in which:
Rs and R7 have the same meanings as R2 defined above;
Re, Rs and R9 have the same meanings as R1 and R3 defined above;
R10 represents a linear or branched, optionally unsaturated alkylene group possibly containing one or more heteroatoms chosen from N, 0, S and P; and
A- is a physiologically acceptable anionic counterion, such as a halide, for instance chloride or bromide, or mesylate.
As regards the meaning of Y, the term “hydrophilic group” means a polymeric or non-polymeric water-soluble group.
By way of example, when it is not a polymer, mention may be made of ethylene glycol, diethylene glycol and propylene glycol.
When it is a hydrophilic polymer, mention may be made, for example, of polyethers, sulfonated polyesters and sulfonated polyamides, or a mixture of these polymers. The hydrophilic compound is preferentially a polyether and notably a poly(ethylene oxide) or polypropylene oxide).
The cationic associative polyurethanes of formula (la) according to the invention are formed from diisocyanates and from various compounds bearing functions containing labile hydrogen. The functions containing labile hydrogen may be alcohol, primary or secondary amine or thiol functions, giving, after reaction with the diisocyanate functions, polyurethanes, polyureas and polythioureas, respectively. In the present invention, the term “polyurethanes” encompasses these three types of polymer, namely polyurethanes per se, polyureas and polythioureas, and also copolymers thereof.
A first type of compound involved in the preparation of the polyurethane of formula (la) is a compound including at least one unit bearing an amine function. This compound may be multifunctional, but the compound is preferentially difunctional, that is to say that, according to a preferential embodiment, this compound includes two labile hydrogen atoms borne, for example, by a hydroxyl, primary amine, secondary amine or thiol function. A mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low may also be used.
As mentioned above, this compound may include more than one unit containing an amine function. In this case, it is a polymer bearing a repetition of the unit containing an amine function.
Compounds of this type may be represented by one of the following formulae: HZ-(P)n-ZH or HZ-(P’)P-ZH, in which Z, P, P’, n and p are as defined above.
Examples that may be mentioned include N-methyldiethanolamine, N-tert- butyldiethanolamine and N-sulfoethyldiethanolamine.
The second compound included in the preparation of the polyurethane of formula (la) is a diisocyanate corresponding to the formula: O=C=N-R4-N=C=O in which R4 is as defined above.
By way of example, mention may be made of methylenediphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, butane diisocyanate and hexane diisocyanate.
A third compound involved in the preparation of the polyurethane of formula (la) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (la).
This compound is constituted of a hydrophobic group and a function containing a labile hydrogen, for example a hydroxyl, primary or secondary amine, or thiol function.
By way of example, this compound may be a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. When this compound includes a polymeric chain, it may be, for example, a-hydroxylated hydrogenated polybutadiene.
The hydrophobic group of the polyurethane of formula (la) may also result from the quaternization reaction of the tertiary amine of the compound including at least one tertiary amine unit. Thus, the hydrophobic group is introduced via the quaternizing agent. This quaternizing agent is a compound of the type RQ or R'Q, in which R and R' are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.
The cationic associative polyurethane may also comprise a hydrophilic block. This block is provided by a fourth type of compound involved in the preparation of the polymer. This compound may be multifunctional. It is preferably difunctional. It is also possible to have a mixture in which the percentage of multifunctional compound is low.
The functions containing labile hydrogen are alcohol, primary or secondary amine or thiol functions. This compound may be a polymer terminated at the chain ends with one of these functions containing labile hydrogen.
By way of example, when it is not a polymer, mention may be made of ethylene glycol, diethylene glycol and propylene glycol. When it is a hydrophilic polymer, mention may be made, for example, of polyethers, sulfonated polyesters and sulfonated polyamides, or a mixture of these polymers. The hydrophilic compound is preferentially a polyether and in particular a poly(ethylene oxide) or polypropylene oxide).
The hydrophilic group termed Y in formula (la) is optional. Specifically, the units containing a quaternary or protonated amine function may suffice to provide the solubility or water-dispersibility required for this type of polymer in an aqueous solution.
Although the presence of a hydrophilic group Y is optional, cationic associative polyurethanes including such a group are, however, preferred.
- (B’) quaternized cellulose derivatives, and in particular:
- i) quaternized celluloses modified with groups including at least one fatty chain, such as linear or branched alkyl, linear or branched arylalkyl or linear or branched alkylaryl groups including at least 8 carbon atoms, or mixtures thereof;
- ii) quaternized hydroxyethylcelluloses modified with groups including at least one fatty chain, such as linear or branched alkyl, linear or branched arylalkyl or linear or branched alkylaryl groups including at least 8 carbon atoms, or mixtures thereof;
- iii) the hydroxyethylcelluloses of formula (lb):
Figure imgf000017_0001
in which:
- R and R’, which may be identical or different, represent an ammonium group - RaRbRcN+ Q- in which Ra, Rb and Rc, which may be identical or different, represent a hydrogen atom or a linear or branched C1-C30, preferentially C1-C20, alkyl group, such as methyl or dodecyl; and Q’ represents an anionic counterion, such as a halide, for instance a chloride or bromide; and n, x and y, which may be identical or different, represent an integer between 1 and 10 000.
The alkyl radicals borne by the above quaternized celluloses i) or hydroxyethylcelluloses ii) preferably include from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.
Mention may also be made, as examples of quaternized alkylhydroxyethylcelluloses bearing Cs to C30 fatty chains, of the product Quatrisoft LM 200® sold by the company Amerchol/Dow Chemical (INCI name: Polyquaternium-24) and the products Crodacel QM® (INCI name: PG-Hydroxyethylcellulose cocodimonium chloride), Crodacel QL® (C12 alkyl) (INCI name: PG-Hydroxyethylcellulose lauryldimonium chloride) and Crodacel QS® (Cis alkyl) (INCI name: PG- Hydroxyethylcellulose stearyldimonium chloride) sold by the company Croda.
Mention may also be made of the hydroxyethylcelluloses of formula (lb) in which R represents a trimethylammonium halide and R’ represents a dimethyldodecylammonium halide; more preferentially, R represents trimethylammonium chloride -(CH3)3N+CI’ and R’ represents dimethyldodecylammonium chloride -(CH3)2(Ci2H25)N+CI’. This type of polymer is known under the trade name Softcat Polymer SL®, such as SL-100, SL-60, SL-30 and SL-5, from the company Amerchol/Dow Chemical, having the INCI name Polyquaternium-67.
More particularly, the polymers of formula (lb) are those of which the viscosity is between 2000 and 3000 cPs inclusive. Preferentially, the viscosity is between 2700 and 2800 cPs inclusive. Typically, Softcat Polymer SL-5 has a viscosity of 2500 cPs, Softcat Polymer SL-30 has a viscosity of 2700 cPs, Softcat Polymer SL-60 has a viscosity of 2700 cPs and Softcat Polymer SL-100 has a viscosity of 2800 cPs.
- (O’) cationic polyvinyllactams, in particular those comprising:
- a) at least one monomer of vinyllactam or alkylvinyllactam type;
- b) at least one monomer of structure (Ic) or (He) below:
Figure imgf000018_0001
in which:
X denotes an oxygen atom or an NR6 radical,
Ri and Re denote, independently of each other, a hydrogen atom or a linear or branched C1-C5 alkyl radical,
R2 denotes a linear or branched C1-C4 alkyl radical,
R3, R4 and Rs denote, independently of each other, a hydrogen atom, a linear or branched C1-C30 alkyl radical or a radical of formula (lllc):
Figure imgf000018_0002
in which:
- Y, Y1 and Y2 denote, independently of each other, a linear or branched C2-C16 alkylene radical,
R7 denotes a hydrogen atom, or a linear or branched C1-C4 alkyl radical or a linear or branched C1-C4 hydroxyalkyl radical,
Rs denotes a hydrogen atom or a linear or branched C1-C30 alkyl radical, p, q and r denote, independently of each other, either the value zero or the value 1 , m and n denote, independently of each other, an integer ranging from 0 to 100 inclusive, x denotes an integer ranging from 1 to 100 inclusive,
Z denotes an anionic counterion of an organic or mineral acid, such as a halide, for instance chloride or bromide, or mesylate; with the proviso that:
- at least one of the substituents R3, R4, R5 or R8 denotes a linear or branched C9- C30 alkyl radical,
- if m or n is other than zero, then q is equal to 1 ,
- if m or n is equal to zero, then p or q is equal to 0.
The cationic poly(vinyllactam) polymers according to the invention may be crosslinked or noncrosslinked and may also be block polymers.
Preferably, the counterion Z’ of the monomers of formula (Ic) is chosen from halide ions, phosphate ions, the methosulfate ion and the tosylate ion.
Preferably, R3, R4 and Rs denote, independently of each other, a hydrogen atom or a linear or branched C1-C30 alkyl radical.
More preferentially, the monomer b) is a monomer of formula (Ic) for which, preferentially, m and n are equal to 0.
The vinyllactam or alkylvinyllactam monomer is preferably a compound of structure (IVc):
Figure imgf000019_0001
in which s denotes an integer ranging from 3 to 6; R9 denotes a hydrogen atom or a linear or branched C1-C5 alkyl radical and R10 denotes a hydrogen atom or a linear or branched C1-C5 alkyl radical, with the proviso that one at least of the radicals R9 and R10 denotes a hydrogen atom.
Even more preferentially, the monomer (IVc) is vinylpyrrolidone.
The cationic poly(vinyllactam) polymers according to the invention may also contain one or more additional monomers, preferably cationic or nonionic monomers.
As compounds that are particularly preferred, mention may be made of the following terpolymers comprising at least: a) one monomer of formula (IVc), b) one monomer of formula (Ic) in which p=1 , q=0, R3 and R4 denote, independently of each other, a hydrogen atom or a C1-C5 alkyl radical and Rs denotes a linear or branched C9-C24 alkyl radical, and c) one monomer of formula (lie) in which R3 and R4 denote, independently of each other, a hydrogen atom or a linear or branched C1-C5 alkyl radical.
Even more preferentially, terpolymers comprising, by weight, 40% to 95% of monomer (a), 0.1 % to 55% of monomer (c) and 0.25% to 50% of monomer (b) will be used. Such polymers are notably described in patent application WO-OO/68282. As cationic poly(vinyllactam) polymers according to the invention, use is in particular made of: vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethyl- methacrylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethyl- methacrylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethyl- methacrylamidopropylammonium tosylate or chloride terpolymers.
The vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethylacrylami dopropylammonium chloride terpolymer is notably sold by the company ISP under the names Styleze W10® and Styleze W20L® (INCI name: Polyquaternium-55). The weight-average molecular mass (Mw) of the cationic poly(vinyllactam) polymers is preferably between 500 and 20 000 000, more particularly between 200 000 and 2 000 000 and preferentially between 400 000 and 800 000.
- (D’) the cationic polymers obtained by polymerization of a mixture of monomers comprising one or more vinyl monomers substituted with one or more amino groups, one or more hydrophobic nonionic vinyl monomers and one or more associative vinyl monomers, such as described in patent application WO 2004/024779.
Among these polymers, mention will more particularly be made of the products from the polymerization of a monomer mixture comprising:
- a di(Ci-C4 alkyl)amino(Ci-C6 alkyl) methacrylate,
- one or more C1-C30 alkyl esters of (meth)acrylic acid,
- a polyethoxylated C10-C30 alkyl methacrylate (20-25 mol of ethylene oxide units),
- a 30/5 polyethylene glycol/polypropylene glycol allyl ether,
- a hydroxy(C2-Ce alkyl) methacrylate, and
- an ethylene glycol dimethacrylate.
Such a polymer is, for example, the compound sold by the company Lubrizol under the name Carbopol Aqua CC® and which corresponds to the INCI name Polyacrylate-1 Crosspolymer.
The nonionic associative polymers are preferably chosen, alone or as a mixture, from:
(1 ) celluloses modified with groups including at least one fatty chain, notably C8-C32 and better still C14-C28 alkyl; preferably from:
- hydroxyethylcelluloses modified with groups including at least one fatty chain, notably C8-C32 and better still C14-C28 alkyl, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22, for instance the cetylhydroxyethylcellulose sold notably under the reference Natrosol Plus Grade 330 CS (C16 alkyls) sold by the company Ashland, or the product Polysurf 67CS sold by the company Ashland,
- hydroxyethylcelluloses modified with polyalkylene glycol alkylphenol ether groups, such as the product Amercell Polymer HM-1500 (polyethylene glycol (15) nonylphenol ether) sold by the company Amerchol, - and mixtures thereof.
(2) hydroxypropyl guars modified with groups including at least one fatty chain, in particular C8-C32 and better still C14-C28 alkyl, such as the product Esaflor HM 22 (C22 alkyl chain) sold by the company Lamberti, and the products RE210-18 (C14 alkyl chain) and RE205-1 (C20 alkyl chain) sold by the company Rhodia;
(3) copolymers of vinylpyrrolidone and of fatty-chain hydrophobic monomers, notably C8-C32 and better still C14-C28 alkyl. Examples that may be mentioned include:
- the vinylpyrrolidone/hexadecene copolymer and notably the products Antaron V216 or Ganex V216 sold by the company ISP;
- the vinylpyrrolidone/eicosene copolymer and notably the products Antaron V220 or Ganex V220 sold by the company ISP;
(4) copolymers of Ci-Ce alkyl methacrylates or acrylates and of amphiphilic monomers including at least one fatty chain, notably a C8-C32 and better still C14-C28 alkyl chain, for instance the oxyethylenated methyl acrylate/stearyl acrylate copolymer sold by the company Goldschmidt under the name Antil 208.
(5) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers including at least one fatty chain, notably a C8-C32 and better still C14-C28 alkyl chain, for instance the polyethylene glycol methacrylate/lauryl methacrylate copolymer.
(6) polyurethane polyethers including in their chain both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks, which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences;
(7) polymers comprising an aminoplast ether backbone having at least one fatty chain, notably C8-C32 and better still C14-C28 alkyl, such as the Pure Thix compounds sold by the company Sud-Chemie.
Preferably, the polyurethane polyethers include at least two hydrocarbon-based lipophilic chains containing from 8 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon-based chains possibly being pendent chains or chains at the end of the hydrophilic block. In particular, it is possible for one or more pendent chains to be envisaged. In addition, the polymer may include a hydrocarbon-based chain at one end or at both ends of a hydrophilic block.
The polyurethane polyethers may be multiblock, in particular in triblock form. The hydrophobic blocks may be at each end of the chain (for example: triblock copolymer bearing a hydrophilic central block) or distributed both at the ends and in the chain (for example, multiblock copolymer). These same polymers may also be graft polymers or star polymers. The fatty-chain nonionic polyurethane polyethers may be triblock copolymers, the hydrophilic block of which is a polyoxyethylenated chain including from 50 to 1000 oxyethylene groups. The nonionic polyurethane polyethers include a urethane bond between the hydrophilic blocks, whence arises the name.
By extension, also included among the nonionic fatty-chain polyurethane polyethers are those in which the hydrophilic blocks are linked to the lipophilic blocks via other chemical bonds.
As examples of nonionic fatty-chain polyurethane polyethers that may be used in the invention, use may also be made of Rheolate 205® bearing a urea function, sold by the company Rheox, or Rheolate® 208, 204 or 212, and also Acrysol RM 184®. Mention may also be made of the product Elfacos T210® containing a C12-C14 alkyl chain, and the product Elfacos T212® containing a C18 alkyl chain, from Akzo. The product DW 1206B® from Rohm & Haas having a C20 alkyl chain and having a urethane bond, provided at a solids content of 20% in water, can also be used.
Use may also be made of solutions or dispersions of these polymers, in particular in water or in an aqueous/alcoholic medium. Mention may be made, as examples of such polymers, of Rheolate® 255, Rheolate® 278 and Rheolate® 244, sold by the company Rheox. Use may also be made of the products DW 1206F and DW 1206J sold by the company Rohm & Haas.
The polyurethane polyethers that may be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci. 271 , 380.389 (1993).
It is even more particularly preferred to use a polyurethane polyether that may be obtained by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and (iii) at least one diisocyanate.
Such polyether polyurethanes are sold in particular by the company Rohm & Haas under the names Aculyn 46® and Aculyn 44® [Aculyn 46® is a polycondensate of polyethylene glycol having 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81 %); Aculyn 44® is a polycondensate of polyethylene glycol having 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%)].
Preferably, the composition comprises one more or nonionic associative polymers, preferentially chosen from polyurethane polyethers.
Preferably, the associative polymer(s) are present in the composition in a total content ranging from 0.01 % to 10% by weight, preferentially from 0.05% to 5% by weight, more preferentially from 0.1 % to 1 .5% by weight, relative to the total weight of the composition. Preferably, the nonionic associative polymer(s) are present in the composition in a total content ranging from 0.01 % to 10% by weight, preferentially from 0.05% to 5% by weight, more preferentially from 0.1 % to 1.5% by weight, relative to the total weight of the composition.
Preferably, the nonionic associative polymer(s) chosen from polyether polyurethanes are present in the composition in a total content ranging from 0.01 % to 10% by weight, preferentially from 0.05% to 5% by weight, more preferentially from 0.1 % to 1 .5% by weight, relative to the total weight of the composition.
Silicones
The composition used according to the invention may optionally comprise one or more silicones, which may be chosen in particular from amino silicones, non-amino silicones and mixtures thereof.
The composition according to the invention may thus comprise one or more non- amino silicones, which may be solid or liquid, preferably liquid (at 25°C, 1 atm), and volatile or non-volatile.
The non-amino silicones that may be used may be soluble or insoluble in the composition according to the invention; they may be in oil, wax, resin or gum form; silicone oils and gums are preferred.
Silicones are notably described in detail in Walter Noll’s Chemistry and Technology of Silicones (1968), Academic Press.
The volatile silicones may be chosen from those with a boiling point of between 60°C and 260°C (at atmospheric pressure) and in particular from: i) cyclic polydialkylsiloxanes including from 3 to 7 and preferably 4 to 5 silicon atoms, such as
- octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5). Mention may be made of the products sold under the name Volatile Silicone 7207 by Union Carbide or Silbione 70045 V 2 by Rhodia, Volatile Silicone 7158 by Union Carbide or Silbione 70045 V 5 by Rhodia;
- cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type having the chemical structure:
Figure imgf000023_0001
Mention may be made of Volatile Silicone FZ 3109 sold by Union Carbide.
- mixtures of cyclic silicones with silicon-derived organic compounds, such as the mixture of octamethylcyclotetrasiloxane and of tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and of 1 ,1’- oxy(2,2,2’,2’,3,3’-hexatrimethylsilyloxy)bisneopentane; ii) linear polydialkylsiloxanes containing 2 to 9 silicon atoms, which generally have a viscosity of less than or equal to 5x1 O’6 m2/s at 25°C, such as decamethyltetrasiloxane.
Other silicones belonging to this category are described in the article published in Cosmetics and Toiletries, Vol. 91 , Jan. 76, pages 27-32 - Todd & Byers Volatile silicone fluids for cosmetics', mention may be made of the product sold under the name SH 200 by the company Toray Silicone.
Among the non-volatile silicones, mention may be made, alone or as a mixture, of polydialkylsiloxanes and notably polydimethylsiloxanes (PDMS or dimethicone), polydiarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, and also nonamino organopolysiloxanes (or organomodified polysiloxanes, or alternatively organomodified silicones) which are polysiloxanes including in their structure one or more non-amino organofunctional groups, generally attached via a hydrocarbon- based group, and preferably chosen from aryl groups, alkoxy groups and polyoxyethylene and/or polyoxypropylene groups.
The organomodified silicones may be polydiarylsiloxanes, notably polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned previously. The polyalkylarylsiloxanes are particularly chosen from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes.
Among the organomodified silicones, mention may be made of organopolysiloxanes including:
- polyoxyethylene and/or polyoxypropylene groups optionally including C6-C24 alkyl groups, such as dimethicone copolyols, and notably those sold by the company Dow Coming under the name DC 1248 or the oils Silwet® L 722, L 7500, L 77 and L 711 from the company Union Carbide; or alternatively (Ci2)alkylmethicone copolyols, and notably those sold by the company Dow Coming under the name Q2-5200;
- thiol groups, such as the products sold under the names GP 72 A and GP 71 from Genesee;
- alkoxylated groups, such as the product sold under the name Silicone Copolymer F-755 by SWS Silicones and Abil Wax® 2428, 2434 and 2440 by the company Goldschmidt;
- hydroxylated groups, for instance polyorganosiloxanes bearing a hydroxyalkyl function;
- acyloxyalkyl groups, such as the polyorganosiloxanes described in patent US-A-4 957 732;
- anionic groups of the carboxylic acid type, as described, for example, in EP 186 507, or of the alkylcarboxylic type, such as the product X-22-3701 E from the company Shin-Etsu; or else of the 2-hydroxyalkylsulfonate or 2- hydroxyalkylthiosulfate type, such as the products sold by the company Goldschmidt under the names Abil® S201 and Abil® S255;
The silicones can also be chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes having trimethylsilyl end groups (CTFA: dimethicone). Among these polydialkylsiloxanes, mention may be made of the following commercial products:
- the Silbione® oils of the 47 and 70 047 series or the Mirasil® oils sold by Rhodia, for instance the oil 70 047 V 500 000;
- the oils of the Mirasil® series sold by Rhodia;
- the oils of the 200 series from Dow Corning, such as DC200 with a viscosity of 60 000 mm2/s;
- the Viscasil® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric.
Mention may also be made of polydimethylsiloxanes having dimethylsilanol end groups (CTFA: dimethiconol), such as the oils of the 48 series from Rhodia.
In this category of polydialkylsiloxanes, mention may also be made of the products sold under the names Abil Wax® 9800 and 9801 by the company Goldschmidt, which are poly(C1 -C20)dialkylsiloxanes.
Products that may be used more particularly in accordance with the invention are mixtures such as:
- mixtures formed from a polydimethylsiloxane with a hydroxy-terminated chain, or dimethiconol (CTFA), and from a cyclic polydimethylsiloxane, also known as cyclomethicone (CTFA), such as the product Q2-1401 sold by the company Dow Coming.
The polyalkylarylsiloxanes are particularly chosen from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes with a viscosity ranging from 1 xW5 to 5x1 O’2 m2/s at 25°C.
Among these polyalkylarylsiloxanes, mention may be made of the products sold under the following names:
- the Silbione® oils of the 70 641 series from Rhodia;
- the oils of the Rhodorsil® 70 633 and 763 series from Rhodia;
- the oil Dow Coming 556 Cosmetic Grade Fluid from Dow Coming;
- the silicones of the PK series from Bayer, such as the product PK20;
- the silicones of the PN and PH series from Bayer, such as the products PN1000 and PH1000;
- certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.
The non-amino silicones that are more particularly preferred according to the invention are polydimethylsiloxanes containing trimethylsilyl end groups (CTFA: dimethicone). The composition according to the invention may comprise one or more amino silicones.
The term “amino silicone” denotes any silicone including at least one primary, secondary or tertiary amine or a quaternary ammonium group.
The amino silicones that may be used according to the present invention may be volatile or non-volatile and cyclic, linear or branched, and preferably have a viscosity ranging from 5 x w6 to 2.5 m2/s at 25°C, for example from 1 x w5 to 1 m2/s.
Preferably, the amino silicone(s) are chosen, alone or as mixtures, from the following compounds:
A) the polysiloxanes corresponding to formula (I):
Figure imgf000026_0001
in which x’ and y’ are integers such that the weight-average molecular mass (Mw) is between 5000 and 500 000 g/mol;
B) the amino silicones corresponding to formula (II): R’aG3-a-Si(OSiG2)n-(OSiGbR’2-b)m-O-SiG3-a -R’a’ (II) in which:
- G, which is identical or different, denotes a hydrogen atom or a phenyl, OH, Ci-Cs alkyl, for example methyl, or Ci-Cs alkoxy, for example methoxy, group;
- a and a’, which may be identical or different, denote 0 or an integer from 1 to 3, in particular 0, with the proviso that at least one from among a and a’ is equal to zero,
- b denotes 0 or 1 , in particular 1 ,
- m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and notably from 49 to 149, and m possibly denoting a number from 1 to 2000 and notably from 1 to 10; and
- R’, which may be identical or different, denotes a monovalent radical of formula - CqH2qL in which q is a number ranging from 2 to 8 and L is an optionally quaternized amino group chosen from the following groups: -NR”-Q-N(R”)2, -N(R”)2, -N+(R”)3 A- , -N+H(R”)2 A -N+H2(R”) A -NR”-Q-N+(R”)H2 A; -NR”-Q-N+(R”)2H A’ and -NR”-Q- N+(R”)3 A in which R”, which may be identical or different, denotes hydrogen, phenyl, benzyl or a saturated monovalent hydrocarbon-based radical, for example a C1-C20 alkyl radical; Q denotes a linear or branched group of formula CrH2r, r being an integer ranging from 2 to 6, preferably from 2 to 4; and A’ represents a cosmetically acceptable anion, notably a halide, such as fluoride, chloride, bromide or iodide.
Preferably, the amino silicones of formula (II) may be chosen from:
(i) the “trimethylsilyl amodimethicone” silicones corresponding to formula (III):
Figure imgf000027_0001
in which m and n are numbers such that the sum (n + m) varies from 1 to 2000, preferably from 20 to 1000, notably from 50 to 600, better still from 50 to 150; it being possible for n to denote a number from 0 to 1999 and notably from 49 to 149 and it being possible for m to denote a number from 1 to 2000 and notably from 1 to 10;
(ii) the silicones of formula (IV) below:
Figure imgf000027_0002
in which:
- m and n are numbers such that the sum (n + m) ranges from 1 to 1000, notably from 50 to 250 and more particularly from 100 to 200; n denoting a number from 0 to 999 and notably from 49 to 249 and more particularly from 125 to 175, and m denoting a number from 1 to 1000, notably from 1 to 10 and more particularly from 1 to 5; and
- Ri , R2 and R3, which may be identical or different, represent a hydroxyl or C1-C4 alkoxy radical, at least one of the radicals R1 to R3 denoting an alkoxy radical. Preferably, the alkoxy radical is a methoxy radical.
The hydroxy/alkoxy mole ratio preferably ranges from 0.2:1 to 0.4:1 and preferably from 0.25:1 to 0.35:1 and more particularly is equal to 0.3:1.
The weight-average molecular mass (Mw) of these silicones preferably ranges from 2000 to 1 000 000 g/mol and more particularly from 3500 to 200 000 g/mol.
(iii) the silicones of formula (V) below:
Figure imgf000028_0001
in which:
- p and q are numbers such that the sum (p + q) ranges from 1 to 1000, in particular from 50 to 350 and more particularly from 150 to 250; p denoting a number from 0 to 999, notably from 49 to 349 and more particularly from 159 to 239, and q denoting a number from 1 to 1000, notably from 1 to 10 and more particularly from 1 to 5; and
- Ri and R2, which are different, represent a hydroxyl or C1-C4 alkoxy radical, at least one of the radicals R1 or R2 denoting an alkoxy radical.
Preferably, the alkoxy radical is a methoxy radical.
The hydroxy/alkoxy mole ratio generally ranges from 1 :0.8 to 1 :1.1 and preferably from 1 :0.9 to 1 : 1 and more particularly is equal to 1 :0.95.
The weight-average molecular mass (Mw) of the silicone preferably ranges from 2000 to 200 000 g/mol, more preferentially from 5000 to 100 000 g/mol and in particular from 10 000 to 50 000 g/mol.
The commercial products comprising silicones of structure (IV) or (V) may include in their composition one or more other amino silicones, the structure of which is different from formula (IV) or (V). A product containing amino silicones of structure (IV) is sold by the company Wacker under the name Belsil® ADM 652. A product containing amino silicones of structure (V) is sold by Wacker under the name Fluid WR 1300®. Another product containing amino silicones of structure (XIV) is sold by Wacker under the name Belsil ADM LOG 1®.
When these amino silicones are used, one particularly advantageous embodiment consists in using them in the form of an oil-in-water emulsion. The oil-in-water emulsion may comprise one or more surfactants. The surfactants may be of any nature but are preferably cationic and/or nonionic. The number-average size of the silicone particles in the emulsion generally ranges from 3 nm to 500 nm. Preferably, notably as amino silicones of formula (V), use is made of microemulsions of which the mean particle size ranges from 5 nm to 60 nm (limits included) and more particularly from 10 nm to 50 nm (limits included). Thus, use may be made according to the invention of the amino silicone microemulsions of formula (V) sold under the names Finish CT 96 E® or SLM 28020® by the company Wacker. (iv) the silicones of formula (VI) below:
Figure imgf000029_0001
in which:
- m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and notably from 50 to 150, n denoting a number from 0 to 1999 and notably from 49 to 149, and m denoting a number from 1 to 2000 and notably from 1 to 10; and
- A denotes a linear or branched alkylene radical containing from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably linear.
The weight-average molecular mass (Mw) of these amino silicones preferably ranges from 2000 to 1 000 000 g/mol and more particularly from 3500 to 200 000 g/mol.
A silicone corresponding to this formula is, for example, Xiameter MEM 8299 Emulsion from Dow Corning.
(v) the silicones of formula (VII) below:
Figure imgf000029_0002
in which:
- m and n are numbers such that the sum (n + m) ranges from 1 to 2000 and in particular from 50 to 150, n possibly denoting a number from 0 to 1999 and notably from 49 to 149, and m possibly denoting a number from 1 to 2000 and notably from 1 to 10; and
- A denotes a linear or branched alkylene radical containing from 4 to 8 carbon atoms and preferably 4 carbon atoms. This radical is preferably branched.
The weight-average molecular mass (Mw) of these amino silicones preferably ranges from 500 to 1 000 000 g/mol and more particularly from 1000 to 200 000 g/mol.
A silicone corresponding to this formula is, for example, DC2-8566 Amino Fluid from Dow Corning;
C) the amino silicones corresponding to formula (VIII):
Figure imgf000030_0001
in which:
- Rs represents a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a C1-C18 alkyl or C2-C18 alkenyl radical, for example methyl;
- Re represents a divalent hydrocarbon-based radical, notably a C1-C18 alkylene radical or a divalent C1-C18, for example Ci-Cs, alkyleneoxy radical linked to the Si via an SiC bond;
- Q’ is an anion such as a halide ion, notably chloride, or an organic acid salt, notably acetate;
- r represents a mean statistical value ranging from 2 to 20 and in particular from 2 to 8; and
- s represents a mean statistical value ranging from 20 to 200 and in particular from 20 to 50.
D) the quaternary ammonium silicones of formula (IX):
Figure imgf000030_0002
in which:
- R7, which may be identical or different, represent a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a C1-C18 alkyl radical, a C2-C18 alkenyl radical or a ring comprising 5 or 6 carbon atoms, for example methyl;
- Re represents a divalent hydrocarbon-based radical, notably a C1-C18 alkylene radical or a divalent C1-C18, for example Ci-Cs, alkyleneoxy radical linked to the Si via an SiC bond;
- Rs, which may be identical or different, represent a hydrogen atom, a monovalent hydrocarbon-based radical containing from 1 to 18 carbon atoms, and in particular a C1-C18 alkyl radical, a C2-C18 alkenyl radical or a radical -R6-NHCOR7; - X’ is an anion such as a halide ion, notably chloride, or an organic acid salt, notably acetate; and
- r represents a mean statistical value ranging from 2 to 200 and in particular from 5 to 100.
These silicones are for example described in patent application EP-A-0 530 974; mention may in particular be made of the silicone having the INCI name: Quaternium 80.
Silicones falling within this category are the silicones sold by the company Goldschmidt under the names Abil Quat 3270, Abil Quat 3272 and Abil Quat 3474;
E) the amino silicones of formula (X):
Figure imgf000031_0001
in which:
- Ri , R2, RS and R4, which may be identical or different, denote a C1-C4 alkyl radical or a phenyl group,
- Rs denotes a C1-C4 alkyl radical or a hydroxyl group,
- n is an integer ranging from 1 to 5,
- m is an integer ranging from 1 to 5, and
- x is chosen such that the amine number ranges from 0.01 to 1 meq/g;
F) the multiblock polyoxyalkylenated amino silicones, of (AB)n type, A being a polysiloxane block and B being a polyoxyalkylenated block including at least one amine group.
Said silicones are preferably formed from repeating units having the following general formulae:
[-(SiMe2O)xSiMe2-R-N(R”)-R’-O(C2H4O)a(C3H6O)b-R’-N(H)-R-] or else
[-(SiMe2O)xSiMe2-R-N(R”)-R’-O(C2H4O)a(C3H6O)b-] in which:
- a is an integer greater than or equal to 1 , preferably ranging from 5 to 200 and more particularly ranging from 10 to 100;
- b is an integer between 0 and 200, preferably ranging from 4 to 100 and more particularly between 5 and 30;
- x is an integer ranging from 1 to 10 000 and more particularly from 10 to 5000;
- R” is a hydrogen atom or a methyl;
- R, which may be identical or different, represent a linear or branched divalent C2- C12 hydrocarbon-based radical, optionally including one or more heteroatoms such as oxygen; preferably, R, which may be identical or different, denote an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical or a CH2CH2CH2OCH2CH(OH)CH2- radical; preferentially, R denote a CH2CH2CH2OCH2CH(OH)CH2- radical; and
- R’, which may be identical or different, represent a linear or branched divalent C2- C12 hydrocarbon-based radical, optionally including one or more heteroatoms such as oxygen; preferably, R’, which may be identical or different, denote an ethylene radical, a linear or branched propylene radical, a linear or branched butylene radical or a CH2CH2CH2OCH2CH(OH)CH2- radical; preferentially, R’ denote -CH(CH3)- CH2-.
The siloxane blocks preferably represent between 50 mol% and 95 mol% of the total weight of the silicone, more particularly from 70 mol% to 85 mol%.
The amine content is preferably between 0.02 and 0.5 meq/g of copolymer in a 30% solution in dipropylene glycol, more particularly between 0.05 and 0.2.
The weight-average molecular mass (Mw) of the silicone is preferably between 5000 and 1 000 000 g/mol and more particularly between 10 000 and 200 000 g/mol.
Mention may notably be made of the silicones sold under the name Silsoft A-843 or Silsoft A+ by Momentive.
G) the amino silicones of formulae (XI) and (XII):
Figure imgf000032_0001
in which:
- R, R’ and R”, which may be identical or different, denote a C1-C4 alkyl group or a hydroxyl group,
- A denotes a C3 alkylene radical; and
- m and n are numbers such that the weight-average molecular mass of the compound is between 5000 and 500 000;
Figure imgf000033_0001
in which:
- x and y are numbers ranging from 1 to 5000; preferably, x ranges from 10 to 2000 and more preferentially from 100 to 1000; preferably, y ranges from 1 to 100;
- Ri and R2, which may be identical or different, preferably identical, denote a linear or branched, saturated or unsaturated alkyl group comprising from 6 to 30 carbon atoms, preferably from 8 to 24 carbon atoms and more preferentially from 12 to 20 carbon atoms; and
- A denotes a linear or branched alkylene radical containing from 2 to 8 carbon atoms.
Preferably, A comprises from 3 to 6 carbon atoms, more preferentially 4 carbon atoms; preferably, A is branched. Mention may be made in particular of the following divalent groups: -CH2CH2CH2- and -CH2CH(CH3)CH2-.
Preferably, R1 and R2 are independent saturated linear alkyl groups comprising 6 to 30 carbon atoms, preferably 8 to 24 carbon atoms and in particular from 12 to 20 carbon atoms; mention may be made in particular of dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups; and preferentially, R1 and R2, which may be identical or different, are chosen from hexadecyl (cetyl) and octadecyl (stearyl) groups.
Preferably, in the silicone of formula (XII):
- x ranges from 10 to 2000 and in particular from 100 to 1000;
- y ranges from 1 to 100;
- A comprises from 3 to 6 carbon atoms and notably 4 carbon atoms; preferably, A is branched; more particularly, A is chosen from the following divalent groups: - CH2CH2CH2 and -CH2CH(CH3)CH2-; and
- R1 and R2 independently are saturated linear alkyl groups comprising from 6 to 30 carbon atoms, preferably from 8 to 24 carbon atoms and in particular from 12 to 20 carbon atoms; notably chosen from dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups; preferentially, R1 and R2, which may be identical or different, are chosen from hexadecyl (cetyl) and octadecyl (stearyl) groups.
A silicone of formula (XII) that is preferred is bis-cetearyl amodimethicone. Mention may be made in particular of the amino silicone sold under the name Silsoft AX by Momentive. H) polysiloxanes and notably polydimethylsiloxanes, including primary amine groups at only one chain end or on side chains, such as those of formula (XIV), (XV)
Figure imgf000034_0001
In formula (XIV), the values of n and m are such that the weight-average molecular mass of the amino silicone is between 1000 and 55 000.
As examples of amino silicones of formula (XIV), mention may be made of the products sold under the names AMS-132, AMS-152, AMS-162, AMS-163, AMS-191 and AMS-1203 by the company Gelest and KF-8015 by the company Shin-Etsu.
In formula (XV), the value of n is such that the weight-average molecular mass of the amino silicone is between 500 and 3000.
As examples of amino silicones of formula (XV), mention may be made of the products sold under the names MCR-A11 and MCR-A12 by the company Gelest.
In formula (XVI), the values of n and m are such that the weight-average molecular mass of the amino silicone is between 500 and 50 000.
As examples of amino silicones of formula (XVI), mention may be made of the aminopropyl phenyl trimethicone sold under the name DC 2-2078 Fluid by the company Dow Coming.
The cosmetic composition according to the invention may also comprise, as silicone, an amino silicone corresponding to formula (XVIII) below:
Figure imgf000035_0001
in which:
- n is a number between 1 and 1000, preferably between 10 and 500, better still between 25 and 100, even better still between 50 and 80;
- m is a number between 1 and 200, preferably between 1 and 100, better still between 1 and 10 and even better still between 1 and 5;
- R’”, which may be identical or different, preferably identical, are saturated or unsaturated, linear or branched, alkyl radicals comprising from 8 to 30 carbon atoms, preferably from 10 to 24 carbon atoms, notably from 12 to 18 carbon atoms; it being possible for said radicals optionally to be substituted with one or more hydroxyl OH groups;
- R’ is a linear or branched divalent alkylene radical containing from 1 to 6 carbon atoms, notably from 2 to 5 carbon atoms;
- R” is a linear or branched divalent alkylene radical containing from 1 to 6 carbon atoms, notably from 1 to 5 carbon atoms.
Preferably, the radicals R’”, which may be identical or different, are saturated linear alkyl radicals comprising from 8 to 30 carbon atoms, preferably from 10 to 24 carbon atoms, notably from 12 to 18 carbon atoms; mention may be made in particular of dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl radicals; preferentially, the radicals R’”, which may be identical or different, are chosen from saturated linear alkyl radicals containing from 12 to 16 carbon atoms, which are notably C13, C14 or C15 radicals, alone or as a mixture, and better still represent a mixture of C13, C14 and C15 radicals.
Preferably, the radicals R’” are identical.
Preferably, R' is a linear or branched, preferably branched, divalent alkylene radical comprising from 1 to 6 carbon atoms, notably from 2 to 5 carbon atoms; notably a - CH2-CH2-CH2-, -CH2-CH(CH3)-CH2- or -CH2-CH2-CH(CH3)- radical.
Preferably, R” is a linear divalent alkylene radical comprising from 1 to 6 carbon atoms, notably from 1 to 4 carbon atoms, in particular a -CH2-CH2- radical.
Preferentially, the composition may comprise one or more silicones of formula (XVIII) in which:
- n is a number between 50 and 80;
- m is a number between 1 and 5;
- R’”, which are identical, are saturated linear alkyl radicals comprising from 12 to 18 carbon atoms;
- R’ is a divalent alkylene radical having from 2 to 5 carbon atoms;
- R” is a linear divalent alkylene radical having from 1 to 4 carbon atoms.
Better still, the composition may comprise one or more silicones of formula (XVIII) in which:
- n is a number between 50 and 80;
- m is a number between 1 and 5;
- R’”, which are identical, are saturated linear alkyl radicals comprising from 13 to 15 carbon atoms;
- R’ is a -(CH2)3-, -CH2-CH(CH3)-CH2- or -CH2-CH2-CH(CH3)- radical, and
- R” is a -(CH2)2- radical.
A most particularly preferred silicone of formula (XVIII) is Bis(C13-15 Alkoxy) PG- Amodimethicone (INCI name). Mention may notably be made of the silicone sold under the name Dowsil 8500 Conditioning Agent by Dow.
Preferably, the amino silicone(s) are chosen, alone or as a mixture, from:
- the amino silicones of formula (II), preferably those in which G denotes a Ci-Cs alkyl and a = a’ = 0; a most particularly preferred silicone of formula (II) being aminopropyl dimethicone, such as the product sold under the name X-22-9686 by Shin-Etsu;
- the quaternary ammonium silicones of formula (IX) above;
- the amino silicones of formula (XVIII) above, notably those in which n is a number of between 50 and 80; m is a number of between 1 and 5; R’”, which are identical, are saturated linear alkyl radicals comprising from 13 to 15 carbon atoms; R’ is a - (CH2)3-, -CH2-CH(CH3)-CH2- or -CH2-CH2-CH(CH3)- radical, and R” is a -(Coradical.
Advantageously, the composition according to the present invention may comprise the silicone(s) in a total content preferably ranging from 0.3% to 5% by weight, better still from 0.4% to 4% by weight, preferentially from 0.6% to 3% by weight and more preferentially from 0.7% to 2.5% by weight, relative to the total weight of the composition.
Advantageously, the composition according to the present invention may comprise the amino silicone(s) in a total content preferably ranging from 0.3% to 5% by weight, better still from 0.4% to 4% by weight, preferentially from 0.6% to 3% by weight and better still from 0.7% to 2.5% by weight, relative to the total weight of the composition. Cationic surfactants
The composition used according to the invention may optionally comprise one or more cationic surfactants.
Said cationic surfactants are non-silicone surfactants, that is to say that they do not contain an Si-0 group.
They are preferably chosen from primary, secondary or tertiary fatty amines, which are optionally polyoxyalkylenated, or salts thereof, and quaternary ammonium salts, and mixtures thereof.
The composition can comprise one or more cationic surfactants chosen, alone or as a mixture, from the following compounds, which are quaternary ammonium salts:
- the compounds corresponding to the general formula (II) below:
Figure imgf000037_0001
in which:
X’ is an anion notably chosen from the group of halides, phosphates, acetates, lactates, (Ci-C4)alkyl sulfates, (Ci-C4)alkylsulfonates or (Ci-C4)alkylarylsulfonates; the groups Ri to R4, which may be identical or different, represent a linear or branched aliphatic group including from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, at least one of the groups R1 to R4 denoting a linear or branched aliphatic group including from 8 to 30 carbon atoms, preferably from 12 to 24 carbon atoms.
The aliphatic groups may include heteroatoms notably such as oxygen, nitrogen, sulfur and halogens. The aliphatic groups are chosen, for example, from C1-C30 alkyl, C1-C30 alkoxy, (C2-C6) polyoxyalkylene, C1-C30 alkylamide, (C12- C22)alkylamido(C2-C6)alkyl, (Ci2-C22)alkyl acetate, and C1-C30 hydroxyalkyl groups.
Among the quaternary ammonium salts of formula (II), the ones that are preferred are tetraalkylammonium salts, for instance dialkyldimethylammonium or alkyltrimethylammonium salts in which the alkyl group includes from about 12 to 22 carbon atoms, in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium or benzyldimethylstearylammonium salts, and also palmitylamidopropyltrimethylammonium salts, stearamidopropyltrimethylammonium salts, stearamidopropyldimethylcetearylammonium salts, or stearamidopropyldimethyl(myristyl acetate)ammonium salts such as those sold under the name Ceraphyl® 70 by the company Van Dyk.
It is preferred in particular to use the chloride, bromide or methyl sulfate salts of these compounds.
- the quaternary ammonium salts of imidazoline, such as those of formula (III):
Figure imgf000038_0001
in which Rs represents an alkenyl or alkyl group including from 8 to 30 carbon atoms, derived for example from tallow fatty acids, Re represents a hydrogen atom, a Ci- 04 alkyl group or an alkyl or alkenyl group including from 8 to 30 carbon atoms, R? represents a C1-C4 alkyl group, Rs represents a hydrogen atom or a C1-C4 alkyl group, X’ is an anion chosen from the group of halides, phosphates, acetates, lactates, alkyl sulfates, alkyl- or alkylaryl-sulfonates in which the alkyl and aryl groups preferably comprise, respectively, from 1 to 20 carbon atoms and from 6 to 30 carbon atoms.
Preferably, Rs and Re denote a mixture of alkenyl or alkyl groups including from 12 to 21 carbon atoms, for example derived from tallow fatty acids, R7 denotes a methyl group and Rs denotes a hydrogen atom.
Such a product is sold, for example, under the name Rewoquat® W 75 by the company Rewo,
- quaternary diammonium or triammonium salts, in particular of formula (IV):
Figure imgf000038_0002
in which:
R9 denotes an alkyl radical including from about 16 to 30 carbon atoms which is optionally hydroxylated and/or optionally interrupted with one or more oxygen atoms,
R10 is chosen from hydrogen or an alkyl radical including from 1 to 4 carbon atoms or a group (R9a)(Rioa)(Rna)N-(CH2)3, with Rga, Rioa, Rua, R11 , R12, R13 and R14, which may be identical or different, chosen from hydrogen or an alkyl radical including from 1 to 4 carbon atoms, and
X’ is an anion chosen from the group of halides, acetates, phosphates, nitrates, (C1- C4)alkyl sulfates, (Ci-C4)alkylsulfonates and (Ci-C4)alkylarylsulfonates, in particular methyl sulfate and ethyl sulfate.
Such compounds are, for example, Finquat CT-P, sold by Finetex (Quaternium 89), and Finquat CT, sold by Finetex (Quaternium 75); - quaternary ammonium salts containing at least one ester function, such as those of formula (V) below:
Figure imgf000039_0001
in which:
Rw is chosen from Ci-Ce alkyl groups and Ci-Ce hydroxyalkyl or dihydroxyalkyl groups;
Rw is chosen from the group R19-C(O)-; groups R20 which are linear or branched, saturated or unsaturated C1-C22 hydrocarbon-based groups; a hydrogen atom;
Rw is chosen from the group R21 -C(O)-; groups R22 which are linear or branched, saturated or unsaturated Ci-Ce hydrocarbon-based groups; a hydrogen atom;
R17, R19 and R21 , which may be identical or different, are chosen from linear or branched, saturated or unsaturated C7-C21 hydrocarbon-based groups; r, s and t, which may be identical or different, are integers having values from 2 to 6; y is an integer ranging from 1 to 10; x and z, which may be identical or different, are integers having a value from 0 to 10;
X’ is a simple or complex, organic or mineral anion; with the proviso that the sum x + y + z is from 1 to 15, that when x is 0 then Rw denotes R20, and that when z is 0 then R denotes R22.
The alkyl groups Rw may be linear or branched, and more particularly linear. Preferably, Rw denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group.
Advantageously, the sum x + y + z is from 1 to 10.
When Rw is a hydrocarbon-based group R20, it may be long and contain from 12 to 22 carbon atoms, or may be short and contain from 1 to 3 carbon atoms.
When Rw is a hydrocarbon-based group R22, it preferably contains 1 to 3 carbon atoms.
Advantageously, R17, R19 and R21 , which may be identical or different, are chosen from linear or branched, saturated or unsaturated C11-C21 hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated C11- C21 alkyl and alkenyl groups.
Preferably, x and z, which may be identical or different, are equal to 0 or 1 .
Advantageously, y is equal to 1 .
Preferably, r, s and t, which may be identical or different, are equal to 2 or 3, and even more particularly are equal to 2.
The anion X’ is preferably a halide (chloride, bromide or iodide) or an alkyl sulfate, more particularly methyl sulfate. However, use may be made of methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion that is compatible with the ammonium bearing an ester function. The anion X’ is even more particularly chloride or methyl sulfate.
In the composition according to the invention, use may be made more particularly of the ammonium salts of formula (V) in which R15 denotes a methyl or ethyl group, x and y are equal to 1 ; z is equal to 0 or 1 ; r, s and t are equal to 2;
R is chosen from the group R19-C(=O)-, methyl, ethyl or C14-C22 hydrocarbon- based groups, and a hydrogen atom;
R is chosen from the group R21 -C(=O)- and a hydrogen atom;
R17, R19 and R21 , which may be identical or different, are chosen from linear or branched, saturated or unsaturated C13-C17 hydrocarbon-based groups, and preferably from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl groups.
Advantageously, the hydrocarbon-based groups are linear.
Mention may be made, for example, of the compounds of formula (V) such as the diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium, monoacyloxyethyldihydroxyethylmethylammonium, triacyloxyethylmethylammonium and monoacyloxyethylhydroxyethyldimethylammonium salts (notably chloride or methyl sulfate), and mixtures thereof. The acyl groups preferably contain 14 to 18 carbon atoms and are derived more particularly from a plant oil such as palm oil or sunflower oil. When the compound contains several acyl groups, these groups may be identical or different.
These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, an alkyldiethanolamine or an alkyldiisopropanolamine, which are optionally oxyalkylenated, with C10-C30 fatty acids or with mixtures of C10-C30 fatty acids of plant or animal origin, or by transesterification of the methyl esters thereof. This esterification is followed by a quaternization using an alkylating agent such as an alkyl halide (preferably a methyl or ethyl halide), a dialkyl sulfate (preferably a methyl or ethyl sulfate), methyl methanesulfonate, methyl paratoluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.
Such compounds are sold, for example, under the names Dehyquart® by the company Henkel, Stepanquat® by the company Stepan, Noxamium® by the company CECA or Rewoquat® WE 18 by the company Rewo-Witco.
The composition according to the invention may contain, for example, a mixture of quaternary ammonium monoester, diester and triester salts with a weight majority of diester salts.
Use may also be made of the ammonium salts containing at least one ester function that are described in patents US-A-4 874 554 and US-A-4 137 180.
Use may be made of behenoylhydroxypropyltrimethylammonium chloride sold by KAO under the name Quatarmin BTC 131 . Preferably, the ammonium salts containing at least one ester function contain two ester functions.
Among the quaternary ammonium salts containing at least one ester function that may be used, it is preferred to use dipalmitoylethylhydroxyethylmethylammonium salts.
The term “fatty amine” means a compound comprising at least one optionally (poly)oxyalkylenated primary, secondary or tertiary amine function, or salts thereof and comprising at least one C6-C30 and preferably Cs-Cso hydrocarbon-based chain. Preferably, the fatty amines of use according to the invention are not (poly)oxyalkylenated.
Fatty amines that may be mentioned include amidoamines. The amidoamines according to the invention may be chosen from fatty amidoamines, it being possible for the fatty chain to be borne by the amine group or by the amido group.
The term “amidoamine” means a compound comprising at least one amide function and at least one primary, secondary or tertiary amine function.
The term “fatty amidoamine” means an amidoamine comprising, in general, at least one Ce-Cso hydrocarbon-based chain. Preferably, the fatty amidoamines of use according to the invention are not quaternized.
Preferably, the fatty amidoamines of use according to the invention are not (poly)oxyalkylenated.
Mention may be made, among the fatty amidoamines of use according to the invention, of the amidoamines of following formula (VI): RCONHR”N(R’)2
(VI) in which:
- R represents a substituted or unsubstituted, linear or branched, saturated or unsaturated monovalent hydrocarbon-based radical containing from 5 to 29 carbon atoms, preferably from 7 to 23 carbon atoms, and in particular a linear or branched C5-C29 and preferably C7-C23 alkyl radical, or a linear or branched C5-C29 and preferably C7-C23 alkenyl radical;
- R” represents a divalent hydrocarbon-based radical containing less than 6 carbon atoms, preferably from 2 to 4 carbon atoms and better still 3 carbon atoms; and
- R’, which may be identical or different, represent a substituted or unsubstituted, saturated or unsaturated, linear or branched, monovalent hydrocarbon-based radical containing less than 6 carbon atoms, preferably from 1 to 4 carbon atoms, preferably a methyl radical.
The fatty amidoamines of formula (VI) are chosen, for example, from oleamidopropyldimethylamine, stearamidopropyldimethylamine, notably the product sold by the company Index Chemical Company under the name Lexamine S13, isostearamidopropyldimethylamine, stearamidoethyldimethylamine, lauramidopropyldimethylamine, myristamidopropyldimethylamine, behenamidopropyldimethylamine, dilinoleamidopropyldimethylamine, palmitamidopropyldimethylamine, ricinoleamindopropyldimethylamine soyamidopropyldimethylamine, avocadoamidopropyldimethylamine cocamidopropyldimethylamine, minkamidopropyldimethylamine oatamidopropyldimethylamine, sesamidopropyldimethylamine tallamidopropyldimethylamine, olivamidopropyldimethylamine palmitamidopropyldimethylamine, stearamidoethyldiethylamine brassicamidopropyldimethylamine and mixtures thereof.
Preferably, the fatty amidoamines are chosen from oleamidopropyldimethylamine, stearamidopropyldimethylamine, brassicamidopropyldimethylamine and mixtures thereof.
The cationic surfactant(s) are preferably chosen from those of formula (II) above, those of formula (V) above, those of formula (VI) above, and mixtures thereof; better still from those of formula (II) above, those of formula (VI) above, and mixtures thereof; even better still from those of formula (II) above.
Preferentially, the cationic surfactant(s) may be chosen from salts such as chlorides, bromides or methosulfates, of tetraalkylammonium, for instance dialkyldimethylammonium or alkyltrimethylammonium salts in which the alkyl group includes from about 12 to 22 carbon atoms, in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium or benzyldimethylstearylammonium salts; dipalmitoylethylhydroxyethylmethylammonium salts such as dipalmitoylethylhydroxyethylmethylammonium methosulfate; and mixtures thereof. Even more preferentially, they are chosen from cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, dipalmitoylethylhydroxyethylmethylammonium methosulfate, and mixtures thereof.
When they are present, the total content of cationic surfactant(s) in the composition according to the invention preferably ranges from 0.1 % to 10% by weight, notably from 0.2% to 8% by weight, better still from 0.3% to 7% by weight, even better still from 0.5% to 5% by weight, relative to the total weight of the composition.
In a preferred embodiment of the invention, the ratio by weight of the total content of cationic surfactant(s) to the total content of compounds of amino acid type is greater than or equal to 1 .
Cationic polymers
The composition used according to the invention may optionally comprise one or more cationic polymers other than the associative polymers described above. This or these cationic polymer(s) are therefore non-associative.
The term “cationic polymer” denotes any non-silicone (not comprising any silicon atoms) polymer containing cationic groups and/or groups that can be ionized into cationic groups and not containing any anionic groups and/or groups that can be ionized into anionic groups.
The cationic polymers that may be employed preferably have a cationic charge density of less than or equal to 5 milliequivalents/gram (meq/g), better still of less than or equal to 4 meq/g.
The cationic charge density of a polymer corresponds to the number of moles of cationic charges per unit mass of polymer under the conditions where the latter is completely ionized. It may be determined by calculation if the structure of the polymer is known, i.e. the structure of the monomers constituting the polymer and their molar proportion or weight proportion. It may also be determined experimentally by the Kjeldahl method.
The cationic polymers that may be used preferably have a weight-average molar mass (Mw) of between 500 and 5x106 approximately and preferably between 103 and 3x106 approximately.
The cationic polymers that may be employed are preferably non-associative.
Among the cationic polymers that may be used, mention may be made of:
(1 ) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and including at least one of the units having the following formulae:
Figure imgf000043_0001
in which:
- R3, which may be identical or different, denote a hydrogen atom or a CH3 radical;
- A, which may be identical or different, represent a linear or branched divalent alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or a hydroxyalkyl group of 1 to 4 carbon atoms;
- R4, Rs and Re, which may be identical or different, represent an alkyl group containing from 1 to 18 carbon atoms or a benzyl radical, preferably an alkyl group containing from 1 to 6 carbon atoms;
- R1 and R2, which may be identical or different, represent a hydrogen atom or an alkyl group containing from 1 to 6 carbon atoms, preferably methyl or ethyl;
- X denotes an anion derived from a mineral or organic acid, such as a methosulfate anion or a halide such as chloride or bromide.
The copolymers of family (1 ) may also contain one or more units derived from comonomers that may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (C1 -C4) alkyls, acrylic or methacrylic acid esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.
Among these copolymers of family (1 ), mention may be made of:
- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide, such as the product sold under the name Hercofloc by the company Hercules,
- copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride, such as the products sold under the name Bina Quat P 100 by the company Ciba Geigy,
- the copolymer of acrylamide and of methacryloyloxyethyltrimethylammonium methosulfate, such as the product sold under the name Reten by the company Hercules,
- quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, such as the products sold under the name Gafquat by the company ISP, for instance Gafquat 734 or Gafquat 755, or alternatively the products known as Copolymer 845, 958 and 937,
- dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as the product sold under the name Gaffix VC 713 by the company ISP,
- vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, such as the products sold under the name Styleze CC 10 by ISP;
- quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers such as the product sold under the name Gafquat HS 100 by the company ISP;
- preferably crosslinked polymers of methacryloyloxy(C1 -C4)alkyltri(C1 - C4)alkylammonium salts, such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homopolymerization or copolymerization being followed by crosslinking with an olefinically unsaturated compound, in particular methylenebisacrylamide. Use may be made more particularly of a crosslinked acrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion comprising 50% by weight of said copolymer in mineral oil. This dispersion is sold under the name Salcare® SC 92 by the company Ciba. Use may also be made of a crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymer comprising approximately 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are sold under the names Salcare® SC 95 and Salcare® SC 96 by the company Ciba. (2) cationic polysaccharides, notably cationic celluloses and galactomannan gums. Among the cationic polysaccharides, mention may be made more particularly of cellulose ether derivatives including quaternary ammonium groups, cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and cationic galactomannan gums.
The cellulose ether derivatives including quaternary ammonium groups are notably described in FR 1 492 597; they are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose that has reacted with an epoxide substituted with a trimethylammonium group.
Mention may notably be made of the polymers sold under the name llcare Polymer JR (JR 400 LT, JR 125 and JR 30M) or LR (LR 400 and LR 30M) by the company Amerchol.
Cationic cellulose copolymers and cellulose derivatives grafted with a water-soluble quaternary ammonium monomer are described notably in patent US 4 131 576; mention may be made of hydroxyalkyl celluloses, for instance hydroxymethyl, hydroxyethyl or hydroxypropyl celluloses notably grafted with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt. Mention may be made most particularly of crosslinked or non-crosslinked quaternized hydroxyethylcelluloses, the quaternizing agent notably possibly being diallyldimethylammonium chloride; and most particularly hydroxypropyltrimethylammonium hydroxyethylcellulose.
Among the commercial products corresponding to this definition, mention may be made of the products sold under the names Celquat L 200 and Celquat H 100 by the company National Starch.
A particularly preferred cationic cellulose that may notably be mentioned is the polymer having the INCI name Polyquaternium-10.
The cationic galactomannan gums are notably described in patents US 3 589 578 and US 4 031 307; mention may be made of cationic guar gums, notably those comprising cationic trialkylammonium groups, notably trimethylammonium. Mention may thus be made of guar gums modified with a 2,3- epoxypropyltrimethylammonium salt (for example a chloride).
Preferably, 2% to 30% by number of the hydroxyl functions of the guar gums bear cationic trialkylammonium groups. Even more preferentially, 5% to 20% by number of the hydroxyl functions of these guar gums are branched with cationic trialkylammonium groups. Among these trialkylammonium groups, mention may most particularly be made of the trimethylammonium and triethylammonium groups. Even more preferentially, these groups represent from 5% to 20% by weight relative to the total weight of the modified guar gum. According to the invention, guar gums modified with 2,3-epoxypropyltrimethylammonium chloride may be used.
Mention may be made in particular of the products having the INCI names Hydroxypropyl guar hydroxypropyltrimonium chloride and Guar hydroxypropyltrimonium chloride. Such products are notably sold under the names Jaguar C13S, Jaguar C15, Jaguar C17 and Jaguar C162 by the company Solvay.
Among the cationic polysaccharides that may be used, mention may also be made of cationic derivatives of cassia gum, notably those including quaternary ammonium groups; in particular, mention may be made of the product having the INCI name Cassia hydroxypropyltrimonium chloride.
(3) polymers formed from piperazinyl units and divalent alkylene or hydroxyalkylene radicals containing linear or branched chains, optionally interrupted with oxygen, sulfur or nitrogen atoms or with aromatic or heterocyclic rings, and also the oxidation and/or quaternization products of these polymers;
(4) water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis- haloacyldiamine, a bis-alkyl halide or alternatively with an oligomer resulting from the reaction of a difunctional compound which is reactive with a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, an epihalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amine group of the polyamino amide; these polyaminoamides can be alkylated or, if they include one or more tertiary amine functions, they can be quaternized;
(5) polyaminoamide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional agents; Mention may be made, for example, of adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl radical includes from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Among these derivatives, mention may be made more particularly of the adipic acid/dimethylaminohydroxypropyl/diethylenetriamine polymers sold under the name Cartaretine F, F4 or F8 by the company Sandoz.
(6) polymers obtained by reacting a polyalkylene polyamine including two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids containing from 3 to 8 carbon atoms; the mole ratio between the polyalkylene polyamine and the dicarboxylic acid preferably being between 0.8:1 and 1.4:1 ; the resulting polyaminoamide being reacted with epichlorohydrin in a mole ratio of epichlorohydrin relative to the secondary amine group of the polyaminoamide preferably of between 0.5:1 and 1.8:1. Polymers of this type are sold in particular under the name Hercosett 57 by the company Hercules Inc. or under the name PD 170 or Delsette 101 by the company Hercules in the case of the adipic acid/epoxy-propyl/diethylenetriamine copolymer.
(7) cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as the homopolymers or copolymers including, as main constituent of the chain, units corresponding to formula (I) or (II):
Figure imgf000047_0002
in which
- k and t are equal to 0 or 1 , the sum k + t being equal to 1 ;
- R12 denotes a hydrogen atom or a methyl radical;
- R10 and R11 , independently of each other, denote a Ci-Ce alkyl group, a C1-C5 hydroxyalkyl group, a C1-C4 amidoalkyl group; or alternatively R10 and R11 may denote, together with the nitrogen atom to which they are attached, a heterocyclic group such as piperidinyl or morpholinyl; R10 and R11 , independently of each other, preferably denote a C1-C4 alkyl group;
- Y’ is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate.
Mention may be made more particularly of the homopolymer of dimethyldiallylammonium salts (for example chloride) (INCI name polyquaternium- 6) for example sold under the name Merquat 100 by the company Nalco and the copolymers of diallyldimethylammonium salts (for example chloride) and of acrylamide (INCI name polyquaternium-7), notably sold under the name Merquat 550 or Merquat 7SPR;
(8) quaternary diammonium polymers comprising repeating units of formula:
Figure imgf000047_0001
- R13, R14, RIS and Rie, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms or C1-C12 hydroxyalkyl aliphatic radicals; or else R13, R14, R15 and R16, together or separately, form, with the nitrogen atoms to which they are attached, heterocycles optionally comprising a second nonnitrogen heteroatom; or else R13, R14, R15 and R16 represent a linear or branched Ci-Ce alkyl radical substituted with a nitrile, ester, acyl, amide or -CO-O-R17-D or -CO-NH-R17-D group, where R17 is an alkylene and D is a quaternary ammonium group;
- A1 and B1 represent linear or branched, saturated or unsaturated, divalent polymethylene groups comprising from 2 to 20 carbon atoms, which may contain, linked to or intercalated in the main chain, one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and
- X’ denotes an anion derived from a mineral or organic acid; it being understood that A1, R13 and R15 can form, with the two nitrogen atoms to which they are attached, a piperazine ring; in addition, if A1 denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 may also denote a group (CH2)n-CO-D-OC-(CH2)p- with n and p, which may be identical or different, being integers ranging from 2 to 20, and D denoting: a) a glycol residue of formula -O-Z-O-, in which Z denotes a linear or branched hydrocarbon-based radical or a group corresponding to one of the following formulae: -(CH2CH2O)x-CH2CH2- and -[CH2CH(CH3)O]y-CH2CH(CH3)- , in which x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization; b) a bis-secondary diamine residue, such as a piperazine derivative; c) a bis-primary diamine residue of formula -NH-Y-NH-, in which Y denotes a linear or branched hydrocarbon-based radical, or else the divalent radical -CH2- CH2-S-S-CH2-CH2-; d) a ureylene group of formula -NH-CO-NH-.
Preferably, X’ is an anion, such as chloride or bromide. These polymers have a number-average molar mass (Mn) generally of between 1000 and 100 000.
Mention may be made more particularly of polymers which are constituted of repeating units corresponding to the formula:
Figure imgf000048_0001
in which R1 , R2, R3 and R4, which may be identical or different, denote an alkyl or hydroxyalkyl radical containing from 1 to 4 carbon atoms, n and p are integers ranging from 2 to 20, and X- is an anion derived from a mineral or organic acid.
A particularly preferred compound of formula (IV) is the one for which R1 , R2, R3 and R4 represent a methyl radical, n = 3, p = 6 and X = Cl, known as Hexadimethrine chloride according to the INCI (CTFA) nomenclature. (9) polyquaternary ammonium polymers comprising units of formula (V):
Figure imgf000049_0001
in which:
- R , R19, R20 and R21 , which may be identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, [3-hydroxyethyl, [3-hydroxypropyl or - CH2CH2(OCH2CH2)POH radical, in which p is equal to 0 or to an integer between 1 and 6, with the proviso that R , R19, R20 and R21 do not simultaneously represent a hydrogen atom,
- r and s, which may be identical or different, are integers between 1 and 6,
- q is equal to 0 or to an integer between 1 and 34,
- X’ denotes an anion such as a halide,
- A denotes a divalent dihalide radical or preferably represents -CH2-CH2-O-CH2- CH2-.
Examples that may be mentioned include the products Mirapol® A 15, Mirapol® AD1 , Mirapol® AZ1 and Mirapol® 175 sold by the company Miranol.
(10) quaternary polymers of vinylpyrrolidone and of vinylimidazole, for instance the products sold under the names Luviquat® FC 905, FC 550 and FC 370 by the company BASF.
(11 ) polyamines such as Polyquart® H sold by Cognis, which is referenced under the name Polyethylene Glycol (15) Tallow Polyamine in the CTFA dictionary;
(12) polymers including in their structure:
(a) one or more units corresponding to formula (A) below:
Figure imgf000049_0002
(b) optionally one or more units corresponding to formula (B) below: (B)
Figure imgf000049_0003
ii-H
O
In other words, these polymers may be notably chosen from homopolymers or copolymers including one or more units derived from vinylamine and optionally one or more units derived from vinylformamide.
Preferably, these cationic polymers are chosen from polymers including, in their structure, from 5 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 95 mol% of units corresponding to formula (B), preferentially from 10 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 90 mol% of units corresponding to formula (B).
These polymers may be obtained, for example, by partial hydrolysis of polyvinylformamide. This hydrolysis may take place in acidic or basic medium.
The weight-average molecular mass of said polymer, measured by light scattering, may range from 1000 to 3 000 000 g/mol, preferably from 10 000 to 1 000 000 and more particularly from 100 000 to 500 000 g/mol.
The polymers including units of formula (A) and optionally units of formula (B) are notably sold under the name Lupamin by the company BASF, for instance, in a nonlimiting manner, the products sold under the names Lupamin 9095, Lupamin 5095, Lupamin 1095, Lupamin 9030 (or Luviquat 9030) and Lupamin 9010.
Preferably, the cationic polymers that may be employed in the context of the invention are chosen, alone or as a mixture, from the polymers of family (1 ) and cationic polysaccharides, notably cationic celluloses, such as Polyquaternium-10; cationic galactomannan gums, notably cationic guar gums; and also mixtures thereof.
When they are present, the composition according to the invention may comprise the cationic polymer(s) in a total amount ranging from 0.01 % to 10% by weight, better still from 0.05% to 5% by weight, even better still from 0.1 % to 2% by weight, relative to the total weight of the composition.
When they are present, the composition according to the invention may comprise the cationic polysaccharide(s) in a total amount ranging from 0.01 % to 10% by weight, better still from 0.05% to 5% by weight, even better still from 0.1 % to 2% by weight, relative to the total weight of the composition.
Nonionic polysaccharides
The composition used according to the invention may optionally comprise one or more nonionic polysaccharides other than the associative polymers described above. This or these nonionic polysaccharides are thus non-associative.
The nonionic polysaccharides are preferably chosen, alone or as a mixture, from celluloses, starches, galactomannans and their nonionic derivatives, notably their ethers or esters.
These polymers may be physically or chemically modified. Mention may be made, as physical treatment, of the temperature and mention may be made, as chemical treatment, of esterification, etherification, amidation and oxidation reactions, in so far as these treatments make it possible to give polymers that are nonionic.
As galactomannans that may be used, mention may be made of nonionic guar gums which can be modified with (poly)hydroxy(Ci-Ce)alkyl groups, notably hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups. These guar gums are well known from the prior art and may be prepared, for example, by reacting corresponding alkene oxides, for instance propylene oxides, with the guar gum so as to obtain a guar gum modified with hydroxypropyl groups. The degree of hydroxyalkylation preferably ranges from 0.4 to 1 .2 and corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on the guar gum.
Such nonionic guar gums optionally modified with hydroxyalkyl groups are, for example, sold under the trade names Jaguar HP8, Jaguar HP60, Jaguar HP120, Jaguar HP105 SGI and Jaguar HP8 SGI by the company Rhodia Chimie.
The botanical origin of the starch molecules that may be used in the present invention may be cereals or tubers. Thus, the starches are chosen, for example, from corn starch, rice starch, cassava starch, barley starch, potato starch, wheat starch, sorghum starch and pea starch. The starches may be chemically or physically modified, notably by one or more of the following reactions: pregelatinization, oxidation, crosslinking, esterification, etherification, amidation, heat treatments.
The starch molecules may be derived from any plant source of starch, in particular such as corn, potato, oat, rice, tapioca, sorghum, barley or wheat. It is also possible to use hydrolysates of the starches mentioned above. The starch is preferably derived from potato.
The nonionic polysaccharides may also be cellulose-based polymers not including a C10-C30 fatty chain in their structure.
According to the invention, the term “cellulose-based” refers to any polysaccharide compound bearing in its structure sequences of glucose residues linked together by (3-1 ,4 bonds; the cellulose-based polymers may be unsubstituted celluloses, and/or derivatives of nonionic celluloses.
Thus, the cellulose-based polymers that may be used according to the invention may be chosen from unsubstituted celluloses, including those in a microcrystalline form, and cellulose ethers. Among these cellulose-based polymers, cellulose ethers, cellulose esters and cellulose ether/esters are distinguished.
Among the nonionic cellulose ethers that may be mentioned are (C1- C4)alkylcelluloses, such as methylcelluloses and ethylcelluloses (for example Ethocel Standard 100 Premium from Dow Chemical); (poly)hydroxy(Ci- C4)alkylcelluloses, such as hydroxymethylcelluloses, hydroxyethylcelluloses (for example Natrosol 250 HHR sold by Aquaion) and hydroxypropylcelluloses (for example Klucel EF from Aquaion); mixed (poly)hydroxy(Ci-C4)alkyl(Ci- C4)alkylcelluloses, such as hydroxypropylmethylcelluloses (for example Methocel E4M from Dow Chemical), hydroxyethylmethylcelluloses, hydroxyethylethylcelluloses (for example Bermocoll E 481 FQ from Akzo Nobel) and hydroxybutylmethylcelluloses. Preferably, the nonionic polysaccharides are chosen, alone or as a mixture, from celluloses, galactomannans and their nonionic derivatives, notably their ethers; and better still, alone or as a mixture, from nonionic guar gums optionally modified with (poly)hydroxy(Ci-Ce)alkyl, in particular hydroxypropyl, groups; and/or celluloses, which are substituted or substituted, and cellulose ethers, such as (Ci- C4)alkylcelluloses and (poly)hydroxy(Ci-C4)alkylcelluloses.
Preferably, the nonionic polysaccharides are chosen, alone or as a mixture, from nonionic guar gums optionally modified with (poly)hydroxy(Ci-Cs)alkyl, notably hydroxypropyl (INCI name: Hydroxypropyl Guar), groups.
When they are present, the composition according to the invention may comprise the nonionic polysaccharide(s) in a total amount ranging from 0.01 % to 10% by weight, better still from 0.05% to 5% by weight, even better still from 0.1 % to 2% by weight, relative to the total weight of the composition.
When they are present, the composition according to the invention may comprise the nonionic polysaccharide(s) chosen from celluloses, galactomannans and their nonionic derivatives, notably their ethers, and mixtures thereof, in a total amount ranging from 0.01 % to 10% by weight, better still from 0.05% to 5% by weight, even better still from 0.1 % to 2% by weight, relative to the total weight of the composition.
In a preferred embodiment, the composition according to the invention may comprise one or more cationic polymers and one or more nonionic polysaccharides; notably one or more cationic polysaccharides and one or more nonionic polysaccharides; better still one or more cationic polysaccharides chosen from cationic guar gums and cationic celluloses, and one or more nonionic guar gums.
Nonionic surfactants
The composition used according to the invention may optionally comprise one or more nonionic surfactants.
Examples of nonionic surfactants that may be mentioned include the following compounds, alone or as a mixture:
- oxyalkylenated (C8-C24)alkylphenols;
- saturated or unsaturated, linear or branched, oxyalkylenated or glycerolated Cs- C40 alcohols, preferably including one or two fatty chains;
- saturated or unsaturated, linear or branched, oxyalkylenated Cs to C30 fatty acid amides;
- esters of saturated or unsaturated, linear or branched, Cs to C30 acids and of polyethylene glycols;
- preferably oxyethylenated esters of saturated or unsaturated, linear or branched, Cs to C30 acids and of sorbitol;
- fatty acid esters of sucrose; - optionally oxyalkylenated alkyl (poly)glycosides (0 to 10 oxyalkylene units) which may comprise from 1 to 15 glucose units;
- saturated or unsaturated oxyethylenated plant oils;
- condensates of ethylene oxide and/or of propylene oxide;
- N-(C8-C3o)alkylglucamine and N-(C8-C3o)acylmethylglucamine derivatives;
- amine oxides.
The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, preferably oxyethylene units.
The number of moles of ethylene oxide and/or propylene oxide preferably ranges from 1 to 250, more particularly from 2 to 100 and better still from 2 to 50; the number of moles of glycerol ranges notably from 1 to 50 and better still from 1 to 10.
Advantageously, the nonionic surfactants according to the invention do not comprise any oxypropylene units.
Preferably, they comprise a number of moles of ethylene oxide ranging from 1 to 250, notably from 2 to 100 and better still from 2 to 50.
As examples of glycerolated nonionic surfactants, use is preferably made of monoglycerolated or polyglycerolated Cs to C40 alcohols, comprising from 1 to 50 mol of glycerol and preferably from 1 to 10 mol of glycerol.
Mention may be made of lauryl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1.5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleyl/cetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.
Among the glycerolated alcohols, it is more particularly preferred to use the Cs to C10 alcohol containing 1 mol of glycerol, the C10 to C12 alcohol containing 1 mol of glycerol and the C12 alcohol containing 1 .5 mol of glycerol.
Nonionic surfactants of alkyl (poly)glycoside type may notably be represented by the following general formula: R1 O-(R2O)t-(G)v in which:
- R1 represents a linear or branched alkyl or alkenyl radical including 6 to 24 carbon atoms and notably 8 to 18 carbon atoms, or an alkylphenyl radical of which the linear or branched alkyl radical includes 6 to 24 carbon atoms and notably 8 to 18 carbon atoms,
- R2 represents an alkylene radical including 2 to 4 carbon atoms;
- G represents a sugar unit including 5 to 6 carbon atoms;
- 1 denotes a value ranging from 0 to 10 and preferably from 0 to 4;
- v denotes a value ranging from 1 to 15 and preferably from 1 to 4.
Preferably, the alkyl(poly)glycoside surfactants are compounds of the formula described above in which:
- R1 denotes a linear or branched, saturated or unsaturated alkyl radical including from 8 to 18 carbon atoms,
- R2 represents an alkylene radical including 2 to 4 carbon atoms;
- 1 denotes a value ranging from 0 to 3 and preferably equal to 0,
- G denotes glucose, fructose or galactose, preferably glucose,
- it being possible for the degree of polymerization, i.e. the value of v, to range from 1 to 15 and preferably from 1 to 4; the mean degree of polymerization more particularly being between 1 and 2.
The glucoside bonds between the sugar units are generally of 1 -6 or 1 -4 type and preferably of 1 -4 type. Preferably, the alkyl(poly)glycoside surfactant is an alkyl(poly)glucoside surfactant. C8/C16 alkyl (poly)glucosides of 1 -4 type, and notably decyl glucosides and caprylyl/capryl glucosides, are most particularly preferred.
Among the commercial products, mention may be made of the products sold by the company Cognis under the names Plantaren® (600 CS/ll, 1200 and 2000) or Plantacare® (818, 1200 and 2000); the products sold by the company SEPPIC under the names Oramix CG 110 and Oramix® NS 10; the products sold by the company BASF under the name Lutensol GD 70, or the products sold by the company Chem Y under the name AGI O LK.
Preferably, use is made of C8/C16 alkyl (poly)glycosides of 1 -4 type, notably as an aqueous 53% solution, such as those sold by Cognis under the reference Plantacare® 818 UP.
The nonionic surfactant(s) used in the composition according to the invention are preferentially chosen, alone or as a mixture, from:
- saturated or unsaturated, linear or branched, oxyethylenated Cs to C40 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 40 mol of ethylene oxide and preferably including one or two fatty chains;
- saturated or unsaturated oxyethylenated plant oils comprising from 1 to 100 and preferably from 2 to 50 mol of ethylene oxide;
- (Cs-C3o)alkyl (poly)glycosides which are optionally oxyalkylenated, preferably with from 0 to 10 mol of ethylene oxide, and which comprise from 1 to 15 glucose units;
- monoglycerolated or polyglycerolated Cs to C40 alcohols, comprising from 1 to 50 mol of glycerol and preferably from 1 to 10 mol of glycerol;
- saturated or unsaturated, linear or branched, oxyalkylenated Cs to C30 fatty acid amides;
- esters of saturated or unsaturated, linear or branched, Cs to C30 acids and of polyethylene glycols;
- preferably oxyethylenated esters of saturated or unsaturated, linear or branched, Cs to C30 acids and of sorbitol;
More preferentially, the nonionic surfactant(s) used in the composition according to the invention are chosen, alone or as a mixture, from: - saturated or unsaturated, linear or branched, oxyethylenated Cs to C40 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 40 mol of ethylene oxide and including one or two fatty chains, notably at least one C8-C20, notably C10-C18, alkyl chain,
- preferably oxyethylenated esters of saturated or unsaturated, linear or branched, Cs to C30 acids and of sorbitol, and
- (Cs-C3o)alkyl(poly)glucosides, which are optionally oxyalkylenated, preferably comprising from 0 to 10 mol of ethylene oxide and comprising 1 to 15 glucose units.
Preferably, the composition according to the invention comprises the nonionic surfactant(s) in a total content ranging from 0.05% to 10% by weight, preferably from 0.1 % to 5% by weight, preferentially from 0.2% to 3% by weight, relative to the total weight of the composition according to the invention.
Fatty substance
The composition used according to the invention may optionally comprise one or more non-silicone fatty substances, which may be chosen from solid fatty substances, liquid fatty substances and mixtures thereof.
The term “non-silicone fatty substance” means a fatty substance not containing any Si-0 bonds.
The term “solid fatty substance” means a fatty substance having a melting point of greater than 25°C, preferably greater than or equal to 28°C, preferentially greater than or equal to 30°C, at atmospheric pressure (1.013 x 105 Pa).
Advantageously, the solid fatty substances that may be used in the present invention are neither (poly)oxyalkylenated nor (poly)glycerolated.
The solid fatty substances may be chosen from solid fatty acids, solid fatty alcohols, solid esters of fatty acids and/or of fatty alcohols, waxes and ceramides, and mixtures thereof.
The term “fatty acid” means a long-chain carboxylic acid comprising from 6 to 40 carbon atoms, preferably from 8 to 30 carbon atoms. The solid fatty acids according to the invention preferentially comprise from 10 to 30 carbon atoms and better still from 14 to 22 carbon atoms. These fatty acids are neither oxyalkylenated nor glycerolated. The solid fatty acids that may be used in the present invention are notably chosen from myristic acid, cetylic acid, stearylic acid, palmitic acid, stearic acid, lauric acid, behenic acid, and mixtures thereof. Said fatty acids are different from the (poly)hydroxylated carboxylic acids comprising from 2 to 8 carbon atoms described previously.
The term “fatty alcohol” means a long-chain aliphatic alcohol comprising from 6 to 40 carbon atoms, preferably from 8 to 30 carbon atoms, and comprising at least one hydroxyl group OH. These fatty alcohols are neither oxyalkylenated nor glycerolated. The solid fatty alcohols may be saturated or unsaturated, and linear or branched, and include from 8 to 40 carbon atoms, preferably from 10 to 30 carbon atoms, better still from 12 to 30 carbon atoms. Preferably, the solid fatty alcohols have the structure R-OH with R denoting a linear alkyl group, optionally substituted with one or more hydroxyl groups, comprising from 8 to 40, preferentially from 10 to 30 carbon atoms, better still from 12 to 30, or even from 12 to 24 atoms and even better still from 14 to 22 carbon atoms. The solid fatty alcohols that may be used are preferably chosen from saturated, and linear or branched, preferably linear and saturated, (mono)alcohols including from 8 to 40 carbon atoms, better still from 10 to 30, or even from 12 to 24 atoms and better still from 14 to 22 carbon atoms.
The solid fatty alcohols that may be used may be chosen, alone or as a mixture, from:
- myristyl alcohol (or 1 -tetradecanol);
- cetyl alcohol (or 1 -hexadecanol);
- stearyl alcohol (or 1 -octadecanol);
- arachidyl alcohol (or 1 -eicosanol);
- behenyl alcohol (or 1 -docosanol);
- lignoceryl alcohol (or 1 -tetracosanol);
- ceryl alcohol (or 1 -hexacosanol);
- montanyl alcohol (or 1 -octacosanol);
- myricyl alcohol (or 1 -triacontanol).
Preferentially, the solid fatty alcohol is chosen from cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, arachidyl alcohol, and mixtures thereof, such as cetylstearyl or cetearyl alcohol. Particularly preferably, the solid fatty alcohol is chosen from cetyl alcohol, stearyl alcohol or their mixtures, such as cetylstearyl alcohol; better still, the solid fatty alcohol is cetylstearyl alcohol.
The solid esters of a fatty acid and/or of a fatty alcohol that may be used are preferably chosen from the esters resulting from C9-C26 fatty carboxylic acid and/or from C9-C26 fatty alcohol.
Preferably, these solid fatty esters are esters of a linear or branched, saturated carboxylic acid including at least 10 carbon atoms, preferably from 10 to 30 carbon atoms and more particularly from 12 to 24 carbon atoms, and of a linear or branched, saturated monoalcohol, including at least 10 carbon atoms, preferably from 10 to 30 carbon atoms and more particularly from 12 to 24 carbon atoms. The saturated carboxylic acids may optionally be hydroxylated, and are preferably monocarboxylic acids.
Esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1 -C22 alcohols and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of C2-C26 dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used.
Mention may notably be made of octyldodecyl behenate, isocetyl behenate, cetyl lactate, stearyl octanoate, octyl octanoate, cetyl octanoate, decyl oleate, hexyl stearate, octyl stearate, myristyl stearate, cetyl stearate, stearyl stearate, octyl pelargonate, cetyl myristate, myristyl myristate, stearyl myristate, diethyl sebacate, diisopropyl sebacate, diisopropyl adipate, di-n-propyl adipate, dioctyl adipate, dioctyl maleate, octyl palmitate, myristyl palmitate, cetyl palmitate, stearyl palmitate, and mixtures thereof.
Preferably, the solid esters of a fatty acid and/or of a fatty alcohol are chosen from C9-C26 alkyl palmitates, notably myristyl, cetyl or stearyl palmitate; C9-C26 alkyl myristates, such as cetyl myristate, stearyl myristate and myristyl myristate; and C9- C26 alkyl stearates, notably myristyl, cetyl and stearyl stearate; and mixtures thereof. Particularly preferably, the solid esters of a fatty acid and/or of a fatty alcohol are chosen from myristyl stearate, myristyl palmitate and mixtures thereof.
For the purposes of the present invention, a wax is a lipophilic compound, which is solid at 25°C and atmospheric pressure, with a reversible solid/liquid change of state, having a melting point greater than about 40°C, which may be up to 200°C, and having in the solid state anisotropic crystal organization. In general, the size of the wax crystals is such that the crystals diffract and/or scatter light, giving the composition that comprises them a more or less opaque cloudy appearance. By bringing the wax to its melting point, it is possible to make it miscible with oils and to form a microscopically homogeneous mixture, but on returning the temperature of the mixture to room temperature, recrystallization of the wax, which is microscopically and macroscopically detectable (opalescence), is obtained.
In particular, the waxes that are suitable for use in the invention may be chosen from waxes of animal, plant or mineral origin, non-silicone synthetic waxes, and mixtures thereof.
Mention may notably be made of hydrocarbon-based waxes, for instance beeswax or modified beeswaxes (cera bellina), lanolin wax and lanolin derivatives, spermaceti; cork fiber or sugarcane waxes, olive tree wax, rice bran wax, carnauba wax, candelilla wax, ouricury wax, esparto grass wax, berry wax, shellac wax, Japan wax and sumac wax, absolute waxes of flowers; montan wax, orange wax, lemon wax, microcrystalline waxes, paraffins, petroleum jelly, lignite and ozokerite; polyethylene waxes, the waxes obtained by Fischer-Tropsch synthesis and waxy copolymers, and also esters thereof.
Mention may also be made of C20 to C60 microcrystalline waxes, such as Microwax HW.
Mention may also be made of the MW 500 polyethylene wax sold under the reference Permalen 50-L Polyethylene.
Mention may also be made of the waxes obtained by catalytic hydrogenation of animal or plant oils containing linear or branched C8-C32 fatty chains. Among these waxes, mention may notably be made of isomerized jojoba oil such as transisomerized partially hydrogenated jojoba oil, notably the product manufactured or sold by the company Desert Whale under the commercial reference Iso-Jojoba-50®, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut kernel oil, hydrogenated lanolin oil and bis(1 , 1 ,1 -trimethylolpropane) tetrastearate, notably the product sold under the name Hest 2T-4S® by the company Heterene.
The waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, such as those sold under the names Phytowax Castor 16L64® and 22L73® by the company Sophim, may also be used.
A wax that may also be used is a C20 to C40 alkyl (hydroxystearyloxy)stearate (the alkyl group comprising from 20 to 40 carbon atoms), alone or as a mixture. Such a wax is notably sold under the names Kester Wax K 82 P®, Hydroxypolyester K 82 P® and Kester Wax K 80 P® by the company Koster Keunen.
It is also possible to use microwaxes in the compositions of the invention; mention may notably be made of carnauba microwaxes, such as the product sold under the name MicroCare 350® by the company Micro Powders, synthetic-wax microwaxes, such as the product sold under the name MicroEase 114S® by the company Micro Powders, microwaxes constituted of a mixture of carnauba wax and polyethylene wax, such as the products sold under the names Micro Care 300® and 310® by the company Micro Powders, microwaxes constituted of a mixture of carnauba wax and of synthetic wax, such as the product sold under the name Micro Care 325® by the company Micro Powders, polyethylene microwaxes, such as the products sold under the names Micropoly 200®, 220®, 220L® and 250S® by the company Micro Powders, and polytetrafluoroethylene microwaxes, such as the products sold under the names Microslip 519® and 519 L® by the company Micro Powders.
The waxes are preferably chosen from mineral waxes, for instance paraffin, petroleum jelly, lignite or ozokerite wax; plant waxes, for instance cocoa butter, shea butter or cork fibre or sugar cane waxes, olive tree wax, rice bran wax, hydrogenated jojoba wax, ouricury wax, carnauba wax, candelilla wax, esparto grass wax, or absolute waxes of flowers, such as the essential wax of blackcurrant blossom sold by the company Bertin (France); waxes of animal origin, for instance beeswaxes or modified beeswaxes (cera bellina), spermaceti, lanolin wax and lanolin derivatives; microcrystalline waxes; and mixtures thereof.
Ceramides, or ceramide analogues, such as glycoceramides, that may be used in the compositions according to the invention, are known; mention may in particular be made of ceramides of classes I, II, III and V according to the Dawning classification.
The ceramides or analogues thereof that may be used preferably correspond to the following formula:
Figure imgf000058_0001
in which: - R1 denotes a linear or branched, saturated or unsaturated alkyl group, derived from C14-C30 fatty acids, it being possible for this group to be substituted with a hydroxyl group in the alpha position, or a hydroxyl group in the omega position esterified with a saturated or unsaturated C16-C30 fatty acid;
- R2 denotes a hydrogen atom or a (glycosyl)n group, a (galactosyl)m group or a sulfogalactosyl group, in which n is an integer ranging from 1 to 4 and m is an integer ranging from 1 to 8;
- R3 denotes a C15-C26 hydrocarbon-based group which is saturated or unsaturated in the alpha position, it being possible for this group to be substituted with one or more C1 -C14 alkyl groups; it being understood that, in the case of natural ceramides or glycoceramides, R3 can also denote a C15-C26 a-hydroxyalkyl group, the hydroxyl group being optionally esterified with a C16-C30 a-hydroxy acid.
Preferentially, ceramides are used for which R1 denotes a saturated or unsaturated alkyl group derived from C14-C30 fatty acids; R2 denotes a galactosyl or sulfogalactosyl group; and R3 denotes a -CH=CH-(CH2)12-CH3 group.
The ceramides that are more particularly preferred are the compounds for which R1 denotes a saturated or unsaturated alkyl derived from C16-C22 fatty acids; R2 denotes a hydrogen atom; and R3 denotes a saturated or unsaturated linear C15 group.
Use may also be made of the compounds for which Ri denotes a saturated or unsaturated alkyl radical derived from C12-C22 fatty acids; R2 denotes a galactosyl or sulfogalactosyl radical and R3 denotes a saturated or unsaturated C12-C22 hydrocarbon-based radical and preferably a -CH=CH-(CH2)i2-CH3 group.
As compounds that are particularly preferred, mention may also be made of 2-N- linoleoylaminooctadecane-1 ,3-diol; 2-N-oleoylaminooctadecane-1 ,3-diol; 2-N- palmitoylaminooctadecane-1 ,3-diol; 2-N-stearoylaminooctadecane-1 ,3-diol; 2-N- behenoylaminooctadecane-1 ,3-diol; 2-N-[2-hydroxypalmitoyl]aminooctadecane- 1 ,3-diol; 2-N-stearoylaminooctadecane-1 ,3,4-triol and in particular N- stearoylphytosphingosine, 2-N-palmitoylaminohexadecane-1 ,3-diol, N- linoleoyldihydrosphingosine, N-oleoyldihydrosphingosine, N- palmitoyldihydrosphingosine, N-stearoyldihydrosphingosine, and N- behenoyldihydrosphingosine, N-docosanoyl-N-methyl-D-glucamine, cetylic acid N- (2-hydroxyethyl)-N-(3-cetyloxy-2-hydroxypropyl)amide and bis(N-hydroxyethyl-N- cetyl)malonamide; and mixtures thereof. N-Oleoyldihydrosphingosine will preferably be used.
As liquid fatty substances that may be used, mention may be made of liquid hydrocarbons, liquid fatty alcohols, liquid esters of fatty acids and/or fatty alcohols other than the triglycerides, oils of triglyceride type of plant or synthetic origin, mineral oils and mixtures thereof.
The liquid fatty substances have a melting point of less than or equal to 25°C, preferably of less than or equal to 20°C, at atmospheric pressure (1 .013 x 105 Pa). Advantageously, the liquid fatty substances are not (poly)oxyalkylenated.
It is recalled that the fatty alcohols, esters and acids more particularly contain at least one saturated or unsaturated, linear or branched hydrocarbon-based group comprising from 6 to 40 and better still from 8 to 30 carbon atoms, which is optionally substituted, in particular with one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
The liquid hydrocarbons may be Ce to Cis liquid hydrocarbons and be linear, branched or optionally cyclic; they are preferably chosen from Cs-C , notably C10- C14, alkanes. Examples that may be mentioned include hexane, cyclohexane, undecane, dodecane, isododecane, tridecane or isoparaffins, such as isohexadecane or isodecane, and mixtures thereof.
The liquid hydrocarbons may also be chosen from those comprising more than 16 carbon atoms, which may be linear or branched, of mineral or synthetic origin; mention may be made of liquid paraffins or liquid petroleum jelly, polydecenes, hydrogenated polyisobutene, such as Parleam®, and mixtures thereof.
The triglyceride oils of plant or synthetic origin may be chosen from liquid fatty acid triglycerides including from 6 to 30 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, capryl ic/capric acid triglycerides, for instance those sold by the company Stearinerie Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, jojoba oil and shea butter oil, and mixtures thereof.
The liquid fatty alcohols may be chosen from linear or branched, saturated or unsaturated alcohols, preferably unsaturated or branched alcohols, including from 6 to 40 carbon atoms and preferably from 8 to 30 carbon atoms. Examples that may be mentioned include octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2- undecylpentadecanol, isostearyl alcohol, oleyl alcohol, linolenyl alcohol, ricinoleyl alcohol, undecylenyl alcohol and linoleyl alcohol, and mixtures thereof.
As regards the liquid esters of fatty acids and/or fatty alcohols other than the triglycerides mentioned above, mention may notably be made of esters of saturated or unsaturated, linear Ci to C26 or branched C3 to C26, aliphatic mono- or polyacids and of saturated or unsaturated, linear Ci to C26 or branched C3 to C26, aliphatic mono- or polyalcohols, the total carbon number of the esters being greater than or equal to 6, more advantageously greater than or equal to 10.
Preferably, for the esters of monoalcohols, at least one from among the alcohol and the acid from which the esters of the invention are derived is branched.
Among the monoesters, mention may be made of dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; isostearyl octanoate; isocetyl octanoate; octyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methyl acetyl ricinoleate; octyl isononanoate; 2-ethylhexyl isononate; octyldodecyl erucate; oleyl erucate; ethyl palmitate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-octyldecyl palmitate; alkyl myristates such as isopropyl 2-octyldodecyl myristate, isobutyl stearate; 2-hexyldecyl laurate, and mixtures thereof.
Preferably, among the monoesters of monoacids and of monoalcohols, use will be made of ethyl palmitate or isopropyl palmitate, alkyl myristates, such as isopropyl or ethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isodecyl neopentanoate, isostearyl neopentanoate and mixtures thereof.
Still within the context of this variant, esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1 -C22 alcohols and esters of monocarboxylic, dicarboxylic or tricarboxylic acids and of C2-C26 dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcohols may also be used.
Mention may notably be made of: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate; tridecyl erucate; triisopropyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate; and polyethylene glycol distearates, and mixtures thereof.
The composition may also comprise, as fatty ester, sugar esters and diesters of C6 to C30 and preferably C12 to C22 fatty acids. It is recalled that the term “sugar” refers to oxygen-bearing hydrocarbon-based compounds bearing several alcohol functions, with or without aldehyde or ketone functions, and which include at least 4 carbon atoms. These sugars may be monosaccharides, oligosaccharides or polysaccharides.
Examples of suitable sugars that may be mentioned include sucrose, glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, notably alkyl derivatives, such as methyl derivatives, for instance methylglucose.
The sugar esters of fatty acids may be chosen notably from the group comprising the esters or mixtures of esters of sugars described above and of linear or branched, saturated or unsaturated C6 to C30 and preferably C12 to C22 fatty acids. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
The esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters, and mixtures thereof. These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates, arachidonates or mixtures thereof notably such as the mixed oleo-palmitate, oleo-stearate and palmito-stearate esters.
More particularly, use is made of monoesters and diesters and notably sucrose, glucose or methylglucose mono- or di-oleates, -stearates, -behenates, -oleopalmitates, -linoleates, -linolenates and -oleostearates, and mixtures thereof.
An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.
Preferably, use will be made of a liquid ester of a monoacid and of a monoalcohol.
Preferably, the fatty substances are chosen from triglyceride oils of plant or synthetic origin, liquid esters of a fatty acid and/or a fatty alcohol other than triglycerides, liquid Ce-Ci8 hydrocarbons, solid fatty alcohols, solid esters of fatty acids and/or of fatty alcohols, and mixtures thereof.
Preferably, the composition according to the invention may comprise the fatty substance(s) in a total amount ranging from 0.1 % to 20% by weight, better still from 1 % to 18% by weight, preferentially from 2% to 15% by weight, even better still from 5% to 12% by weight, relative to the total weight of the composition.
Additional compounds
The composition used according to the invention advantageously comprises water, notably in a concentration preferably ranging from 50% to 95% by weight, for example from 55% to 90% by weight, notably from 60% to 85% by weight, better still from 65% to 85% by weight, relative to the total weight of the composition.
The pH of the composition may be between 2.5 and 8, preferentially between 3 and 7, or even between 4 and 6.
The composition used according to the invention may optionally comprise one or more preferably hydrophilic (water-soluble or water-miscible) organic solvents which are liquid at 25°C, 1 atm, which may be chosen from Ci-Ce aliphatic or aromatic monoalcohols, C2-C8 polyols and C3-C7 polyol ethers. Advantageously, the organic solvent is chosen from C2-C4 mono-, di- or tri-diols. It may advantageously be chosen from ethanol, isopropanol, benzyl alcohol, glycerol, 1 ,2-propanediol (propylene glycol) and mixtures thereof.
The composition used according to the invention may also comprise at least one or more standard cosmetic ingredients notably chosen from thickeners, gelling agents, which are both different from the polymers described above; sunscreens; antidandruff agents; antioxidants; chelating agents; reducing agents; oxidation bases, couplers, oxidizing agents, direct dyes; hair-straightening agents; nacreous agents and opacifiers; micas, nacres, glitter flakes; plasticizers or coalescers; pigments; fillers; fragrances; basifying or acidifying agents; silanes. A person skilled in the art will take care to select the ingredients included in the composition, and also the amounts thereof, so that they do not harm the properties of the compositions of the present invention.
According to a preferred embodiment of the invention, the hair composition used in the process according to the invention may comprise:
- one or more compounds of amino acid type corresponding to formula (I) as defined above, in which p = 2 and R represents a hydrogen atom or a saturated, linear or branched, (Ci-C4)alkyl group, optionally interrupted with a -S- heteroatom and/or optionally substituted with one or two groups chosen from hydroxyl, amino or -NH- C(NH)-NH2; better still, R represents a hydrogen atom; preferably present in a total content from 0.6% to 10% by weight, notably from 0.7% to 8% by weight, better still from 0.8% to 7% by weight, relative to the total weight of the composition;
- one or more hydroxylated polycarboxylic acids, comprising from 4 to 6 carbon atoms, from 1 to 3 OH groups and 2 or 3 COOH groups, and/or salts thereof, preferably present in a total content from 0.5% to 10% by weight, notably from 1 % to 8% by weight, better still from 1 .5% to 6% by weight;
- optionally one or more associative polymers which are preferably nonionic, better still chosen from polyether polyurethanes; preferably present in the composition in a total content ranging from 0.01 % to 10% by weight, preferentially from 0.05% to 5% by weight, more preferentially from 0.1 % to 1 .5% by weight, relative to the total weight of the composition;
- optionally one or more silicones, preferably chosen from amino silicones; preferably present in a total content ranging from 0.3% to 5% by weight, better still from 0.4% to 4% by weight, preferentially from 0.6% to 3% by weight and more preferentially from 0.7% to 2.5% by weight, relative to the total weight of the composition;
- optionally one or more cationic surfactants preferably chosen from those of formula (II) above, those of formula (V) above, those of formula (VI) above, and their mixtures, better still from those of formulae (II) and/or of formula (VI) above; preferably present in a total amount ranging from 0.1 % to 10% by weight, better still from 0.2% to 8% by weight, preferentially from 0.3% to 7% by weight, even better still from 0.5% to 5% by weight, relative to the total weight of the composition;
- optionally one or more cationic polysaccharides, notably chosen from cationic celluloses and/or galactomannan gums; preferably present in a total amount ranging from 0.01 % to 10% by weight, better still from 0.05% to 5% by weight, even better still from 0.1 % to 2% by weight, relative to the total weight of the composition;
- optionally one or more nonionic polysaccharides, notably chosen, alone or as a mixture, from nonionic guar gums optionally modified with (poly)hydroxy(Ci-Ce)alkyl groups; preferably present in a total amount ranging from 0.01 % to 10% by weight, better still from 0.05% to 5% by weight, even better still from 0.1 % to 2% by weight, relative to the total weight of the composition;
- optionally one or more nonionic surfactants; preferably present in a total content ranging from 0.05% to 10% by weight, preferably from 0.1 % to 5% by weight, preferentially from 0.2% to 3% by weight, relative to the total weight of the composition according to the invention.
The examples that follow serve to illustrate the invention without, however, being limiting in nature. Unless otherwise indicated, all the amounts are indicated as mass percentages of active material (g% AM) relative to the total weight of the composition.
Example 1
The following composition A according to the invention and the following comparative composition A’ were prepared from the ingredients shown in the tables below (g% AM):
[Table 1 ]
Figure imgf000064_0001
Composition A is in the form of a cream and may advantageously be used in rinse- out mode after or before shampooing. This composition may be used for disentangling of the hair, with the addition of care, sheen and strength (slightly less suppleness than classic care treatments, body and a mass effect).
The hair is soft, hydrated and more shiny; it is considered stronger and less prone to breakage.
The composition thus has strengthening properties and makes it possible to reduce the amount of calcium contained in the hair fibre application after application.
The strengthening is measured using the DSC technique.
(i) preparation of the locks
The measurements are performed on locks that have previously been bleached manually and then treated five times (or ten times) according to the following protocol: the lock is washed with a neutral shampoo, then rinsed, 2 g of the composition to be tested are applied to each 5.7 g lock of hair, the treatment is left on for 5 minutes, then rinsed again.
(ii) measurement method
The differential scanning calorimetry (DSC) technique is known to those skilled in the art as a method for quantifying the strengthening of proteins in the cortex of keratin fibres (Kinetics of the changes imparted to the main structural components of human hair by thermal treatment, F.-J. Wortmann and H. Deutz, J. Appl. Polym Sci. , 48, 137 (1993). The principle of the test is to measure the protein denaturing temperature. It is widely acknowledged that the higher the protein denaturing temperature, the better the integrity of the proteins of the cortex, which reflects the reduction in fibre breakage.
The denaturing temperature is directly linked to the bonding density of the keratin proteins present in the cortex. Thus, the lower the denaturing temperature, the lower the bonding density between the proteins: the disulfide bridges break and the cortex is damaged. A difference of 2°C is acknowledged by those skilled in the art as a significant modification.
The machine used for taking the measurements is a TA Instruments DSC Q20 reference instrument. This machine measures the energy flow during heating of the sample. The temperature of maximum energy flow represents the denaturing temperature.
(iii) results
The results of the denaturing temperature (Td) measurements for each of the locks treated according to the protocol described previously are summarized in the table below and correspond to the mean of three measurements taken per lock.
[Table 2]
Figure imgf000065_0001
Figure imgf000066_0001
These results show that the use of the composition according to the invention increases the bonding density of the keratin proteins presents in the cortex of the treated hair, thus enabling repair of the damaged hair.
Moreover, the denaturing temperature for the locks treated according to the present invention is better than that measured for natural, undamaged hair, thus demonstrating that the hair has been repaired.
This result is improved application after application.
Calcium analysis by X-ray fluorescence according to the RC-ANA-MET-1414 method.
These tests are carried out on locks bleached beforehand and then treated ten times according to the following protocol: the lock is washed with a neutral shampoo, is then rinsed, 2 g of test composition are applied per lock of hair of 5.7 g, the care composition is left to stand for 5 minutes and then rinsing is again carried out.
The following results are obtained:
[Table 3]
Figure imgf000066_0002
It is thus found that the concentration of calcium decreases significantly for the locks treated with the invention.
Example 2
The following composition according to the invention was prepared from the ingredients shown in the tables below (g% AM):
[Table 4]
Figure imgf000066_0003
Figure imgf000067_0001
The composition is in the form of a lotion and may advantageously be used, without rinsing, before shampooing or after shampooing and before using a mask or a hair conditioner without rinsing.
This composition can be used for disentangling the hair, with the addition of care, sheen and strength (body and mass effect).
The hair is soft, hydrated and more shiny; it is considered stronger and less prone to breakage.
The composition thus has strengthening properties and makes it possible to reduce the amount of calcium contained in the hair fibre application after application.
The strengthening is measured by DSC, according to the method described above. The measurements are performed on locks previously bleached manually and then treated five (or ten) times according to the following protocol: the lock is washed with a conventional neutral shampoo, then rinsed, 2 g of the composition according to the invention are applied per 5.7 g lock of hair, and then, without rinsing, 2 g of a conventional hair mask are applied, the mask is left on for 5 minutes and then rinsed once again.
This routine according to the invention is compared with the following comparative routine (without application of the composition of the invention): the lock is washed with a conventional neutral shampoo, then rinsed, 2 g of a conventional hair mask (the same as in the routine according to the invention) are applied, the mask is left on for 5 minutes and then rinsed again.
The following results are obtained (mean of three measurements per lock):
Table 5]
Figure imgf000067_0002
Figure imgf000068_0001
These results show that the use of the composition according to the invention increases the bonding density of the keratin proteins presents in the cortex of the treated hair, thus enabling repair of the damaged hair.
Calcium analysis by X-ray fluorescence according to the RC-ANA-MET-1414 method.
These measurements are performed on the locks treated according to the routine of the invention and according to the comparative routine described above.
The following results are obtained:
[Table 6]
Figure imgf000068_0002
It is thus seen that the calcium concentration reduces significantly for the locks treated according to the invention, application after application.

Claims

1. Cosmetic hair treatment process, comprising at least two successive steps of applying a cosmetic composition comprising:
- one or more compounds of amino acid type present in a total content of at least 0.6% by weight, relative to the total weight of the composition, and
- one or more hydroxylated polycarboxylic acids comprising from 2 to 8 carbon atoms, and/or salts thereof, present in a total content of at least 0.5% by weight, relative to the total weight of the composition.
2. Process according to the preceding claim, in which the compounds of the amino acid type are chosen from the compounds corresponding to formula (I) and/or salts thereof, notably alkali metal or alkaline-earth metal salts, or zinc salts:
Figure imgf000069_0001
in which p is an integer equal to 1 or 2, it being understood that:
- when p = 1 , R forms, with the nitrogen atom, a saturated heterocycle comprising from 5 to 8 ring members, preferably 5 ring members, it being possible for this ring to be substituted with one or more groups chosen from hydroxyl or (Ci-C4)alkyl;
- when p = 2, R represents a hydrogen atom or a saturated, linear or branched, (Ci- Ci2)alkyl, preferably (Ci-C4)alkyl, group, optionally interrupted with one or more heteroatoms or groups chosen from -S-, -NH- or -C(NH)- and/or optionally substituted with one or more groups chosen from hydroxyl (-OH), amino (-NH2), - SH, -COOH, -CONH2 or -NH-C(NH)-NH2; preferably in which p = 2 and R represents a hydrogen atom or a saturated, linear or branched, (Ci-C4)alkyl group, optionally interrupted with a -S- heteroatom and/or optionally substituted with one or two groups chosen from hydroxyl, amino or -NH- C(NH)-NH2; better still, p = 2 and R represents a hydrogen atom.
3. Process according to either of the preceding claims, in which the compound(s) of amino acid type are chosen from glycine, proline, methionine, serine, arginine, lysine, their salts, in particular alkali metal, alkaline-earth metal or zinc salts, and mixtures thereof; preferentially chosen from glycine, its salts, in particular alkali metal, alkaline-earth metal or zinc salts, and mixtures thereof.
4. Process according to one of the preceding claims, in which the total content of compound(s) of amino acid type ranges from 0.6% to 10% by weight, notably from 0.7% to 8% by weight, better still from 0.8% to 7% by weight, relative to the total weight of the composition.
5. Process according to one of the preceding claims, in which the composition comprises one or more hydroxylated polycarboxylic acids, comprising four to six carbon atoms, one to three OH groups and two to three COOH groups; and/or salts thereof, notably alkali metal, alkaline-earth metal or zinc salts; preferably chosen from tartaric acid and/or citric acid, and salts thereof, notably alkali metal or alkaline- earth metal salts; most particularly sodium citrate and/or sodium tartrate; better still citric acid or its salts, notably alkali metal or alkaline-earth metal salts, such as sodium citrate.
6. Process according to one of the preceding claims, in which the total content of hydroxylated polycarboxylic acids comprising in total from 2 to 8 carbon atoms, and/or salts thereof, ranges from 0.5% to 10% by weight, notably from 1 % to 8% by weight, better still from 1.5% to 6% by weight, relative to the total weight of the composition.
7. Process according to one of the preceding claims, in which the composition comprises one or more associative polymers which are preferably nonionic, preferentially chosen from polyether polyurethanes; notably in a total content ranging from 0.01 % to 10% by weight, preferentially from 0.05% to 5% by weight, more preferentially from 0.1 % to 1.5% by weight, relative to the total weight of the composition.
8. Process according to one of the preceding claims, in which the composition comprises one or more silicones, preferably chosen from amino silicones; notably in a total content ranging from 0.3% to 5% by weight, better still from 0.5% to 4% by weight, preferentially from 0.6% to 3% by weight and more preferentially from 0.7% to 2.5% by weight, relative to the total weight of the composition.
9. Process according to one of the preceding claims, in which the composition comprises one or more cationic surfactants, notably in a total amount ranging from 0.1 % to 10% by weight, better still from 0.2% to 8% by weight, preferentially from 0.3% to 7% by weight, even better still from 0.5% to 5% by weight, relative to the total weight of the composition.
10. Process according to one of the preceding claims, in which the composition comprises one or more cationic polymers, preferably chosen from cationic polysaccharides, notably cationic celluloses, cationic galactomannan gums, notably cationic guar gums; and also mixtures thereof; in particular in a total amount ranging from 0.01 % to 10% by weight, better still from 0.05% to 5% by weight, even better still from 0.1 % to 2% by weight, relative to the total weight of the composition.
11. Process according to one of the preceding claims, in which the composition comprises one or more nonionic polysaccharides, notably chosen, alone or as a mixture, from celluloses, galactomannans and their nonionic derivatives, in particular their ethers; better still, alone or as a mixture, from nonionic guar gums optionally modified with (poly)hydroxy(Ci-Ce)alkyl groups, notably hydroxypropyl groups, and/or celluloses, which are substituted or unsubstituted, and cellulose ethers, such as (Ci-C4)alkylcelluloses and (poly)hydroxy(Ci-C4)alkylcelluloses; preferentially chosen, alone or as a mixture, from nonionic guar gums optionally modified with (poly)hydroxy(Ci-Ce)alkyl, notably hydroxypropyl, groups; preferably in a total amount ranging from 0.01 % to 10% by weight, better still from 0.05% to 5% by weight, even better still from 0.1 % to 2% by weight, relative to the total weight of the composition.
12. Process according to one of the preceding claims, in which the composition comprises one or more nonionic surfactants, notably in a total content ranging from 0.05% to 10% by weight, preferably from 0.1 % to 5% by weight, preferentially from 0.2% to 3% by weight, relative to the total weight of the composition according to the invention.
13. Process according to one of the preceding claims, in which the composition comprises one or more non-silicone fatty substances, preferably chosen from triglyceride oils of plant or synthetic origin, liquid esters of a fatty acid and/or of a fatty alcohol other than triglycerides, liquid Ce-C hydrocarbons, solid fatty alcohols, solid esters of fatty acids and/or of fatty alcohols, and mixtures thereof; notably in a total amount ranging from 0.1 % to 20% by weight, better still from 1 % to 18% by weight, preferentially from 2% to 15% by weight, better still from 5% to 12% by weight, relative to the total weight of the composition.
14. Process according to one of the preceding claims, comprising a rinsing step, for example with water or with a shampoo, after a possible leave-on time, between each successive step of applying the composition.
15. Process according to one of the preceding claims, for treating the hair, in particular for washing and/or conditioning sensitized, embrittled and/or damaged hair, or hair laden with metals, in contents of at least 100 ppm, better still of at least 200 ppm; in particular laden with copper, notably in contents of at least 100 ppm, better still of at least 200 ppm, and/or laden with calcium, notably in contents of at least 4000 ppm, better still of at least 10 000 ppm.
PCT/EP2023/064403 2022-06-01 2023-05-30 Cosmetic hair treatment process, comprising a multi-application of a composition comprising amino acids and specific hydroxy carboxylic acids WO2023232788A1 (en)

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